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Alcohols Section - 1
The compounds in which hydroxyl group (OH) is attached to a saturated carbon atom are called as
Alcohols. The compounds in which a hydroxyl group is attached to an unsaturated carbon atom of a double
bond are called as Enols. The saturated carbon may be that of an alkyl, alkenyl, alkynyl, cycloalkyl or
benzyl group. However if a hydroxyl group is attached to a benzene ring, the compounds are called as
Phenols.
The alcohols are further classified as : Monohydric (containing one OH group), Dihydric (containing two
OH groups) and Trihydric (containing three OH groups).
Monohydric alcohols are further classified as: Primary (1) RCH2OH, Secondary (2) R2CHOH, Tertiary
(3) R3COH.
Preparations of Alcohols
1. Hydrolysis of alkyl halides : Alkyl halides undergo hydrolysis when heated with aqueous alkalies or
moist silver oxide. The hydrolysis occurs by a nucleophillic substitution reaction.
H O
2 R OH NaX
R X NaOH
C2 H5 Br KOH aq
C2 H5 OH KBr
Sometimes this method is not satisfactory as Olefins (alkenes) are also formed as side products
specially if halide is tertiary. If R is 3, then alkyl halides mainly give alkenes, when NaOH is concen
-trated (–OH as base).
However satisfactory results are obtained by using moist Silver oxide (AgOH) or aqueous K2CO3.
RI AgOH
R OH Ag I
2. From alkenes :
(a) By acid-catalysed hydration of alkenes : Alkenes react with cold concentrated H2SO4
to give alkyl hydrogen sulphates following Markonikov’s addition.
2 CH C H CH H O
CH 3 CH CH 2 H OSO3H
CH 3 C H CH 3 3 3
Propene Cold | |
OSO3H OH
Isopropylhydrogensulphate
Note : Alkyl hydrogen sulphate when boiled with water give alcohols.
(b) Hydroboration - Oxidation of alkenes : Alkenes react with diborane in presence of THF as sol
vent to form alkyl boranes (Hydroboration). Alkyl boranes are then oxidised and hydrolysed by the
addition of hydrogen peroxide in aqueous base.
2 6 1.B H /THF
CH 3CH CH 2 CH 3 C H C H 2
| |
2.H 2 O 2 /OH ,H OH
H OH
Here the net addition (syn) of H – OH to alkenes is in accordance with Anti-Markonikov’s rule and
free from any rearrangement. It is an important method for preparing 1 alcohols.
Note : In the above reaction, ‘H’ comes from B2 H6 and ‘OH’ comes from H 2O molecule.
H
1. Hg OAc 2 / THF, H OH
|
R CH CH 2
R C H C H2
2. NaBH 4 , OH |
OH
(2 Alcohol)
The above reaction (anti) occurs in accordance with Markonikov’s addition (unlike Hydroboration
reaction). The ‘H’ becomes attached to the carbon atom of the double bond with greater number of
hydrogen atoms. It too does not involve rearrangement.
Note : In the above reaction, ‘OH’ comes from H 2O and ‘H’ comes from NaBH 4 .
3. Reduction of Aldehydes and Ketones : Aldehydes and Ketones on reduction yield alcohols. A
number of reducing agents like H2/Ni, Pt, Pd or Na/C2H5OH or Zn/HCl or LiAlH4 in ether or
NaBH4 in alkali can be used for this purpose.
(a) Bouveault - Blanc reduction : The reducing agent used is sodium and ethanol. The aldehyde
and ketones are reduced by nascent hydrogen into corresponding alcohols.
Na
RCHO 2 H RCH 2OH (1° alcohol)
EtOH
(b) Reduction with LiAlH4 : It is better reducing agent for the conversion of carbonyl com-
pounds into alcohols. LiAlH4 is soluble in ether, the common solvent and it does not reduce
the carbon - carbon double bond.
LiAlH
4 CH CH CHCH OH
CH 3 CH CH CHO 2 H 3 2
ether
Note : (i) NaBH4 also does not reduce carbon - carbon double bond. Also, NaBH 4 is a mild reducing agent.
(ii) Catalytic hydrogenation reduces carbon – carbon double bond as well as carbonyl group.
Ni
CH 2 CHCHO 4 H
CH 3CH 2CH 2OH
Catalyst
(iii) Ketones are reduced to secondary alcohols by Aluminium isopoxide in Isopropyl alcohol. The reduc
-tion by this method is known as Meerwin-Pondorrf-Verley (MPV) reduction and is considered as
an important method for the formation of secondary alcohols.
CH3 CH O Al
2 3
R 2C O R 2CH OH
in Isopropyl alcohol
(iv) As a special case, LiAlH 4 also reduces double bond if conjugated with a phenyl group, in ,
unsatured carbonyl compound along with carbonyl group.
4 LiAlH
Ph CH = CH CHO Ph CH 2 CH 2 CH 2OH
ether
(v) NaBH 4 can reduce aldehydes, ketones and acyl chlorides to alcohols.
LiAlH 4 can reduce carboxylic acids, esters (to alcohols) and amides (to amines) also.
* H
or OH *
R CO O R ' H OH R 'O H RCOOH
Alcohols being more volatile than acids can be easily separated by distillation.
5. From Ethers :
(a) Hydrolysis : Ethers when heated with dil. sulphuric acid under pressure are hydrolysed to the
corresponding alcohols.
H SO
2 4 ROH R 'OH
R OR ' H 2O (Separated by fractional distillations)
dil.
Note : (i) The details of this reaction are given in Section - 3 (Ethers)
(ii) In this reaction, refluxing the products with KI(aq) gives only alcohols.
HI KI/ H
C 2 H 5OCH 3 C 2 H 5OH CH 3I
C 2 H 5OH CH 3OH
HI (aq)/ H
6. Action of Nitrous acid on primary amines : Primary alcohols are formed when primary amines
(only) are treated with nitrous acid (HNO2).
RNH 2 HONO
ROH N 2 H 2O
C2 H5 NH 2 HNO2
C2 H5OH N 2 H 2O
Note : Under similarly conditions, Methylamine does not yield Methanol. The product formed is Methylnitrite or
Dimethyl ether.
CH3 NH 2 2 HNO 2
CH3 O N O 2H 2O N 2
or 2CH3 NH 2 2HNO 2
CH 3 O CH 3 3H 2O 2 N 2
(c) Reduction by LiAlH4 : The acids can be reduced to primary alcohols by LiAlH4
(not by NaBH4).
1. LiAlH in ether
4
RCOOH RCH 2OH
2. H O 2
Esters are more easily reduced than carboxylic acids by LiAlH4. Two alcohols are formed
from each ester molecule; one is derived form the acyl part and other from the alcoholic part.
O
|| 1. LiAlH 4
R C OR ' R CH 2OH R 'OH
2. H O 2
8. From Grignard Reagent : All the three types of monohydric alcohols can be prepared by the use
of Grignard reagents.
(a) Primary alcohols : Primary alcohols are obtained when Grignard reagent is reacted with
oxygen or Formaldehyde or Ethylene oxide.
(i)
The alcohol has same number of carbon atoms as present in the alkyl group of the
Grignard reagent.
(ii)
The alcohol has one carbon atom more than the alkyl group of the Grignard reagent.
(iii)
The alcohol has two carbon atoms more than the alkyl group of the Grignard reagent.
(b) Secondary alcohols : Secondary alcohols are obtained when Grignard reagent is reacted
with an aldehyde other than formaldehyde.
(i) 2 alcohols are obtained when Grignard reagent is reacted with an aldehyde other
than formaldehyde.
(ii) Formate esters on treatment with Grignard reagent first forms aldehyde which then
reacts with second molecule of Grignard reagent and forms secondary alcohols.
(ii) Esters on treatment with Grignard reagent first forms ketone which then reacts with
second molecule of Grignard reagent and forms tertiary alcohols.
9. Industrial Methods :
(a) Methanol : [CH3OH : Also known Carbinol or wood spirit]
(i) Destructive distillation of wood
Methanol (Natural method)
300 C
CO 2H 2 CH 3OH
200 atm
From molasses, both glucose and fructose are formed, which are converted to ethyl alcohol
by zymase.
2 nH O Maltase
2 C6 H10O5 n n C12 H 22O11 n C6 H12O 6 n C6H12O 6
Diastase H 2O
Starch Maltose Glucose Fructose
From starch, both glucose and fructose are formed, which are converted to ethyl alcohol by
zymase.
Note : Absolute alcohol (100% pure ethyl alcohol). Rectified spirit (containing 95.87 % C2H5OH + 4.13 % H2O)
cannot be converted into absolute alcohol simply by distillation because the mixture of ethanol and water in
the ratio of 95.87 : 4.13 (a ratio present in rectified spirit) is a constant boiling mixture (azeotropic mixture)
having b.p. 78.13C.
Methylated spirit (Denaturated alcohol) It is rectified spirit (industrial alcohol) mixed with poisonous sub-
stances like CH3OH, pyridine, acetone, etc. to make it unfit for drinking purposes. The usual composition
of denatured alcohol is 8590% rectified spirit + 1015% methanol.
Power alcohol. Alcohol used for the generation of power is called power alcohol. It is a mixture of petrol
and alcohol in the ratio of 4 : 1 in presence of benzene or ether.
Physical Properties
1. The lower alcohols are readily soluble in water and the solubility decreases with the increase in molecu-
lar weight. The solubility of alcohols in water can be explained due to the formation of hydrogen bond
between the highly polarised –OH groups present both in alcohol and water.
H O.........H O.........H O
| | |
H H H
Relative solubility of isomeric alcohols in water is 1 > 2 > 3.
2. Boiling points of alcohols are much higher than those of the corresponding alkanes and ethers. It is due to
the formation of hydrogen bonding between the hydroxyl groups of the two molecules of an alcohol with
the result several molecules are associated to form a large molecules.
H O ............ H O ............ H O
| | |
H H H
3. Lower alcohols form solid addition compounds with anhydrous metallic salts like CaCl2 and MgCl2, viz.,
CaCl2.4C2H5OH and MgCl2.6C2H5OH.
By analogy to water of crystallisation, these alcohol molecules are referred to as alcohol of crystallisation.
For this reason, alcohols cannot be dried over anhydrous calcium chloride.
4. Methanol is highly toxic. Ingestion of even small quantities of methanol can cause blindness ; large quantities
can cause death. Methanol poisoning can also occur by inhalation of the vapours or by prolonged exposure
to the skin. Ethanol is a hypnotic (sleep producer). Ethanol is much less toxic than methanol.
Reactions of Alcohols
Let us examine the electron distribution in the alcoholic functional group,
and its impact on the reactivity :
(i) Oxygen atom of an alcohol polarizes both CO bonds and the OH bond of an alcohol. Polarization
of the OH bond makes the hydrogen partially positive and explains why alcohols are weak acids.
In such reactions alcohols act as acids and cleavage of the OH bond takes place. The order of
reactivity of different alcohols for such reactions is :
CH3OH > 1 > 2 > 3 alcohols.
(ii) Polarisation of the CO bond makes the carbon atom partially positive, and hence it would have
been susceptible to nucleophilic attack if OH– were not a strong base, i.e., if OH– were not a poor
leaving group.
Protonated alcohols easily undergo nucleophilic substitution which may be SN2 or SN1 depending
upon the class of alcohol.
Note that alcohols do not give typical nueleophilic substitution reaction since OH ion being a strong base
is a poor leaving group.
But alcohols do give nucleophilic substitution in presence of halogen acids. In presence of acids, leaving
group is H 2O instead of OH group. Primary alcohols having carbon as 1 or 2 always give
S N 2 reaction. Secondary alcohols having carbon as 1 also give S N 2 reaction. All tertiary alcohols
give S N 1 reaction.
S N 1 path :
+
1st step : HX
(CH3 )3 C OH
(CH3 )3 C OH 2
fast
2nd step :
Note that it is almost similar to S N 1 in alkyl halides. Allyl and benzyl alcohols also follow the same path
(S N 1).
HX +
S N 2 path : RCH 2OH
RCH 2 O H 2
Note : (i) In SN 2 reactions, X being weak base do not bring elimination by removing hydrogen. How
ever in SN 1 reaction, carbocations formed may lose proton to give alkenes (EI).
(ii) Another method to bring out substitution in alcohols especially by SN 2 path is to convert them into
halides with PX3 or into sulphonates with TsCl.
(iii) At a high temperature, and in the absence of a good nucleophile, protonated alcohols are capable of undergo-
ing elimination reactions.
2 R O M H2
2 ROH 2 M (where M Na, K, Mg, Al, etc.)
RO Na H 2O
ROH NaOH
(iv) Since most alcohols are weaker acids than water, most alkoxide ions are stronger bases than the
hydroxide ions. (CH3)3 CO > C2H5O > OH > CH3O (Relative basic character).
Alcohols as acids
Alcohols have acidities similar to that of water. Methanol is a slightly stronger acid than water but most
alcohols are somewhat weaker acids. In general, the order of acidity of alcohols is as follows :
H 2O > CH3CH 2OH > (CH3 )2 CH OH > (CH3 )3 C OH.
The reason sterically hindered alcohols such as tert-butyl alcohol are less acidic arises from solvation effects.
With unhindered alcohols, water molecules are able to surround and solvate the negative oxygen of the alkoxide
ion formed when an alcohol loses a proton. Solvation stabilizes the alkoxide ion and increases the acidity of
the alcohol. Any factor that stabilizes the conjugate base of an acid increases its acidity.
If the R– group of the alcohol is bulky, solvation of the alkoxie ion is hindered, and the alkoxide ion is not as
effectively stabilized. The alcohol, consequently, is a weaker acid.
All alcohols, however, are much stronger acids than terminal alkynes, and are very much stronger acids than
hydrogen, ammonia, and alkanes.
Relative Acidity H2O > ROH > RC CH > NH3 > RH > H2
The conjugate base of an alcohol is an alkoxide ion. Sodium and potassium alkoxide can be prepared by
treating alcohols with sodium or potassium metal or with the metal hydride. Because most alcohols are weaker
acids than water, most alkoxide ions are stronger bases than the hydroxide ion.
Relative basicity H– > R– > NH2– > RC C– > RO– > OH–
Alcohols reacts with diazomethylene in presence of BF3 , Grignard reagent due to acidic nature.
+ BF
3 ROCH + N
ROH+ C H 2 N N 3 2
Ether
ROH + CH3 MgBr CH 4 + ROMgBr
Unlike the reaction with carboxylic acids, these reactions are irreversible, hence yields of esters via
this route are always high.
(iv) Reaction with acyl chlorides or acid anhydrides is used to determine number of hydroxyl groups in
polyhydric alcohols.
Molar mass of product Molar mass of polyhydric alcohol
Number of OH groups =
42
(v) Suitable hydroxycarboxylic acid undergoes intramolecular esterification to form cyclic ester. (Called
as Lactone)
The mechanism of the reaction will be discussed in Carboxylc Acids.
(c) Esters of Inorganic acids : Alcohols react with inorganic acids, viz. HNO3, H2SO4, H3PO3
and H3PO 4 to form esters of inorganic acids.
H
ROH HONO 2 RONO 2 H 2O
2CH3OH + H 2CO3 (CH3 )2 CO3 Dimethyl carbonate
H 2O
CH OH
3 CH OSO OCH
CH 3OH HO SO 3H
CH 3OSO3H 3 2 3
Methyl hydrogen sulphate Dimethyl sulphate
The order of reactivity of the hydrogen halides is HI > HBr > HCl (HF is generally unreac
tive), and the order of reactivity of alcohols is 3° > benzyl allyl > 2° > 1° > CH 3 . This
reaction follows nucleophillic substitution mechanism.
Note : The mixture of HCl and anhydrous ZnCl2 at room temperature is called Lucas reagent and the reaction is
referred to as LUCAS TEST. (appearance of a white turbid solution). 3 alcohols give Lucas Test instantly
; 2 alcohols give it after sometime and 1 alcohols do not give this test.
Note : Mechanism : Secondary, tertiary, allylic, and benzylic alcohols appear to react by SN1 mechanism.
Step 1 :
Step 2 :
Step 3 :
Most of the primary alcohols and methyl alcohol react by SN2 mechanism.
R OH SOCl 2
R Cl SO 2 HCl
SNi
If reaction takes place on chiral carbon atom then product is formed with retention in configuration because
reaction proceed by intramolecular nucleophilic substitution (SN i) reaction mechanism.
Note : The reaction of alcohols with phosphorus and Sulphur halides involves no rearrangement unlike with HX.
4. Dehydration to Alkenes : Alcohols on reaction with conc. H2SO4/, H3PO4 or catalysts such as anhy-
drous zinc chloride or alumina, loose the water molecule and form alkenes.
conc. H SO excess
2 4
C 2 H 5OH
CH 2 CH 2
170 C
2 4 conc. H SO excess
CH 3CH 2 C H CH 3 CH 3CH CHCH 3 CH 3CH 2CH CH 2
| Major Minor
OH
The ease of dehydration is 3 > 2 > 1 alcohols.
The Dehydration always follow Saytzeff rule.
Al O
2 3 CH CH
In gas phase, alcohols are heated with alumina to give alkene. C 2 H 5OH
2 2
350 C
5. Reaction with Ammonia : When a mixture of the vapours of an alcohol and ammonia are passed over
heated alumina or thoria catalyst at 360C, a mixture of primary, secondary and tertiary amines is pro-
duced.
Al O
2 3 RNH ROH ROH
ROH NH 3 2 R 2 NH R 3N
360 C Al 2 O3 Al 2 O3
1amine 2°amine 3°amine
Re d P
7. Reduction : ROH 2HI RH I 2 H 2O
8. Oxidation : The oxidation of alcohols is used to distinguish between 1, 2, 3 alcohols.
O
1 alcohols : RCH 2OH
O
RCHO RCOOH
25C
aldehyde acids
2 alcohols :
O
3 alcohols : R 3C OH do not oxidise
Tertiary alcohols do not undergo oxidation reaction. Under strong reaction conditions such as strong oxidising
agents (KMnO4) and elevated temperatures, cleavage of various C–C bonds takes place and a mixture of
carboxylic acids containing lesser number of carbon atoms is formed.
The important oxidising agents are : KMnO4/H+, Na2Cr2O7/H+, Chromic acid (H2CrO4). Some examples
are :
2 H CrO
4 CH CHO
2 4 CH COOH H CrO
CH 3CH 2OH 3 3 ;
Note : (i) H2CrO4 does not oxidises double or triple bond in alcohols unlike KMnO4 and K2Cr2O7.
OH O
| H 2 CrO 4
||
H 2C CH C H CH 3 H 2C CH C CH 3
(ii) Cycloalkanols in presence of 50% HNO3 at 55C undergo cleavage forming dioic acids.
(iii) It is difficult to stop oxidation at aldehydic stage in aqueous solution. Hence a special oxidising agent,
Pyridinium chlorochromate (PCC) in CH2Cl2, is used to convert alcohols to aldehydes.
PCC
CH 2 CH CH 2CH 2OH
CH 2 CH CH 2CHO
CH 2Cl 2
PCC only oxidises 1 and 2 alcohols, not unsaturated bonds. PCC does not oxidise 3 alcohols. It
is however mainly used for 1 alcohoos.
(iv) Manganese dioxide selectively oxidises the alcoholic group of allylic and benzylic 1 and 2 alcohols
to give aldehydes and ketones respectively.
MnO
2 CH CH CH CHO
CH 3 CH CH CH 2 OH 3
MnO
2 C H CHO
C 6H 5 CH 2 OH 6 5
(v) Jones Reagent : H2CrO4 in acetone at 35C oxidises 1 and 2 alcohols to aldehydes and ketones
respectively. It, however does not oxidise double bond. It is mainly used for 2 alcohols.
Cu
2 alcohols : CH 3 C H OH CH 3 C O H 2
573 K 2
|
CH 3
Cu
3 alcohols : CH3 3 C OH CH3 2 C CH 2 H 2O (Alkenes are formed)
573 K
10.Lucas Test : Lucas reagent (a mixture of conc. HCl and ZnCl2) reacts with alcohols to form correspond-
ing alkyl chlorides which are soluble.
2 ZnCl
1 alcohols : RCH 2OH No reaction at room temperature.
HCl
ZnCl
2 R C Cl
2 alcohols : R 2CH OH 3 White turbidity after 5 – 10 minutes.
HCl
ZnCl
2 R C Cl
3 alcohols : R 3C OH 3 White turbidity instantaneously.
HCl
Note : Allyl and Benzyl alcohol reacts as rapidly as 3alcohol to form soluble chloride with Lucas reagent.
Function of ZnCl2 in Lucas reagent : Since chloride ion is a weaker nucleophilie than bromide or iodide
ions, HCl does not react with less reactive 1 and 2 alcohols unless some good Lewis acid like ZnCl2 is
added to the reaction mixture. Zinc chloride, a good Lewis acid, forms a complex withthe alcohol. The
complex provides a better leaving group for the reaction than H2O.
(i) In case of 2 and 3 alcohols, the function of acid is to help in the formation of carbocations.
(ii) In case of methyl and 1 alcohols, the function of acid is to produce a substrate in which the leaving
group is a weakly basic species ; H2O or [Zn(OH)Cl2]– rather than a strongly basic hydroxide ion.
(ii) 3and Benzyl alcohols are more reactive due to formation of more stable corresponding carbocations.
11. Victor Meyer Test : This test is based upon the fact that three types (1, 2 and 3) of nitroalkanes
(formed by alcohols) react differently with nitrous acids followed by the action of Sodium hydroxide(alkali).
P/I
2 RCH I AgNO
2 RCH NO
2 R – C – NO HNO
1° Alcohol : RCH 2OH 2 2 2 2
or HI ||
NOH
Nitrolic acid
Pseudonitrol on treatment with alkali does not dissolve but gives blue colour.
P /I 2
2 R C I AgNO 2 No reaction. HNO
3° Alcohol : R 3C OH 3 R 3C NO 2
PHENOLS Section - 2
Phenols are compounds containing an hydroxyl group : OH group, attached directly to an aromatic ring.
These generally are derivative of main member phenol, C6H5OH (ph – OH). The compounds in which OH
group is not attached directly to the ring such as benzyl alcohol, C6H5CH2OH are not phenols. These are
called as side chain aromatic alcohols having properties similar to aliphatic alcohols.
Some important phenols are :
Preparation of Phenols
1. From Chlorobenzene :
3. From Cumene :
II.
III.
5. From Benzene :
Reactions of Phenol
(A) Reactions of –OH group :
1. Salt Formation : Phenol is a weak acid and turns FeCl3 solution violet, but fails to give litmus
test. It reacts with sodium and NaOH to give phenoxides. Phenol however does not react with
Na2CO3 and NaHCO3.
The reaction of phenol with aqueous sodium hydroxide indicates that phenols are stronger acids
than alcohols and water.
2. Formation of Ester : The acetylation and benzoylation of phenols are called as Shautan-Bauman
reactions.
3. Formation of Ethers :
6. Oxidation :
7. Condensation with Pthalic anhydride : Phenol undergoes a special Friedal Craft acylation with
pthalicanhydride in presence of H2SO4 to form phenolphthalein (an acid-base neutralisation indica-
tor).
8. With NH3 :
Note : Halogenation of phenol takes place even in absence of Lewis acid (AlBr3 , FeBr3 ) due to the highly activat
-ing effect of OH group.
Note : OH group is strongly activating, hence a tri-substituted product is formed. However, in CS2 at 0C, only
Ortho (o) and Para (p) derivatives are formed.
2. Nitration :
Note : With concentrated nitric acid, phenol forms 2, 4, 6 - Trinitrophenol, commonly known as Picric acid.With
dilute acid, however, a mixture of o- and p- nitrophenol is formed. This mixture can be separated by
steam distillation.
3. Sulphonation :
At 25C, phenol gives only o-hydroxy benzene sulphonic acid, whereas at 100C, it gives p-hydroxy
benzene sulphonic acid.
Picric acid is prepared in good yield by treating phenol first with concentrated H 2SO 4 which con-
verts it to phenol-2, 4-disulphonic acid, then with concentrated HNO3 to get 2, 4, 6-trinitrophenol.
4. Nitrosation :
5. Alkylation :
Phenols undergo Friedal Craft alkylation to give the product according to the most stable intermedi-
ate carbonium ion.
Mechanism of Reimer – Tiemann Reaction: The reaction involves electrophillic substitution on the
highlyreactive phenoxide ring. Here the electrophile is dichlorocarbene : CCl2 , generated from CHCl3 by
the action of a base.
7. Kolbe’s Reaction :
Note : (i) Transition state is stabilized by small size of (ii) If the reaction is carried out on potassium phenox-
Na + ion. ide the salt of the p-acid becomes the major prod
uct.
The salicyclic acid formed above in Kolbe’s reaction is used to produce a number of important derivatives
used as medicines.
ETHERS Section - 3
In ethers, the oxygen atom is bonded to two carbon atoms. The hydrocarbon group may be alkyl (1, 2
and 3), allylic, vinyl, alkynyl or aryl. Consider some examples :
CH3 – O – CH3 C2H5 – O – CH3 CH2 = CH – O – CH3
Dimethyl ether Ethyl methyl ether (Phenetole) Methyl vinyl ether
There are various types of cyclic ethers. Cyclic ethers consisting of two carbons in a three member ether are
called oxirane or epoxides. Cyclic ethers consisting of three carbons in a four member ether are called
oxetanes. Cyclic ethers consisting of four carbons in a five member ether are called tetrahydrofurans.
Preparations of Ethers
1. From alcohols : Dehydration of alcohols by H2SO4 at 170C gives alkenes, whereas at 140C
gives ethers. The dehydration of alcohols to ether is helped by distilling the ether as it is formed.
H SO
2 4 CH CH
CH 3CH 2OH 2 2 (Alkene)
170 C
H SO
2 4 CH CH O CH CH
CH 3CH 2OH 3 2 2 3 (Ether)
140C
The formation of ethers occurs by SN2 mechanism with one molecule of alcohols acting as the nucleo
phile and another protonated molecules of the alcohols acting as the substrate. The mechanism of the
reaction is given below.
Step : 1 The alcohol accepts a proton from the acid to give a protonated alcohol.
Step : 2 The other molecule of alcohol acts a nucleophile and attacks the protonated alcohol in an
SN2 reaction to give a protonated ether.
Step : 3 The protonated ether transfers the proton to water molecule to give ether.
Note : (i) In case, when alkyl groups are 3, SN1 type path is followed. 3 alkyl alcohol forms a carbocation
(stable) and second alcohol acting as a nucleophile adds to it (solvolysis). An elimination product is
also formed as a minor product.
CH 3 CH 3 CH 3 CH 3
| | H 2SO 4
| |
CH 3 C OH CH 3 C OH
140C
CH 3 C O C H CH 3 CH 3 2 C CH 2
| | | (Minor product)
CH 3 H CH 3
(ii) This method is generally limited to the preparation of symmetrical ethers, because a combination of
two alcohols usually yields a mixture of three ethers.
2. Williamson’s Synthesis : This is the most important method of formation of ethers (nucleophillic substitu
tion reaction), also known as Williamson’s synthesis. It consists of SN2 attack by alkoxide ion on an alkyl
halide, alkyl sulphate or alkyl sulphonate.
The alkoxide ion reacts with substrate in an SN2 reaction to give an ether. The substrate must have a good
leaving group. Important leaving groups are : halides (X), sulphates (OSO2OR) and sulphonates
(OSO2R). The substrate must have a primary alkyl group for good yield. In case of tertiary substrate,
elimination occurs. The other factor which contributes to substitution is low temperature.
Note : The aromatic ethers are formed when phenoxides reacts with alkyl sulphates in an SN2 reaction.
C 6 H 5 O Na CH 3 OSO 2O CH 3
C 6 H 5OCH 3 NaOSO 2OCH 3
Sodium phenoxide Dimethyl sulphate Methyl phenyl ether
2 3 Al O
2ROH g
R O R H 2O
260 280 C
vapours
4. Oxymercuration - Demercuration :
Note : If water is used instead of alcohols and acid, an alkene is formed as per Markonikov’s addition.
5. By the action of Diazomethane : Methyl ethers can also be prepared by the action of diazomethane
(CH2N2) on alcohols in presence of HBF4 as catalyst.
4 HBF
CH 3CH 2OH CH 2 N 2 CH 3CH 2 O CH 3 N 2
6. From Grignard Reagents : Higher ethers can be prepared by treating -halo ethers with suitable Grignard
reagents. For example,
Dry
CH 3 O CH 2CH 3 Mg I Cl
CH 3 O CH 2Cl CH 3MgI
ether
2(CH 3 ) 2 CHCl Ag 2O
(CH 3 ) 2 CH O CH(CH 3 ) 2 2 AgCl
Reactions of Ethers
Ethers are in general are less reactive and react only with acids. The reactive sites in ethers are : C – H
bonds (as in alkanes) and – O – group of ether bond. Ethers resist the attack of nucleophiles and bases.
However ethers are very good solvents in many organic reactions due to their ability to solvate cations by
donating the electron pair from oxygen atom.
1. Halogenation of ethers : Ethers like alkanes undergo halogenation in dark to give halogenated
ethers. The hydrogen atom attached to the carbon atom directly linked to oxygen atom is replaced
by halogens.
Cl
2 CH CH O C HCH
2 CH C H O C HCH Cl
CH 3CH 2 O CH 2CH 3 3 2 3 3 3
| | |
Cl Cl Cl
2. Ethers as Base : The oxygen atom of ethers makes them basic. They react with a proton donor to
give oxonium salts.
H
|
CH 3CH 2 O CH 2CH 3 Br
CH 3CH 2 O CH 2CH 3 H Br
3. Reaction with acids :
Ethers undergo cleavage under quite vigorous conditions, such as concentrated acids (usually HI and
HBr) and high temperatures.
R O R ' HX RX R 'OH
If the acid is present in excess, then the alcohol formed, further reacts with HX to give a halide
(Nucleophillic substitution).
A di-alkyl ether (symmetric ether) yields two alkyl halide molecules, if HX is present is excess,
under hot conc. conditions.
R O R HX
ROH RX ; ROH HX
RX H 2O
HX
R O R
2 RX
excess
( hot conc.)
(i) In case when both alkyl groups are 1 or 2 (i.e. R or R ' 3 ), then SN2 path occurs.
I– as a nucleophile attacks the smaller of the two alkyl groups to give an alkyl iodide.
As I– makes an SN2 attack, consider steric factors. So, the smaller of the alkyl groups
goes with the iodide ion and the larger group forms alcohols.
(ii) If any one of R or R is 3, then we have different products via different mechanism. Here SN1
type of path is followed. Let R be 3.
H slow
R ' O R
R ' O R R 'OH R (3 carbocation, highly stable)
step
|
H
R I
RI (Hence 3R forms iodide)
Phenols do not react further to give halide (Nucleophillic substitution does not take place in aromatic
compounds).
Important :
Since it is SN2 path, X– should be a strong nucleophile. Hence in cleavage of aromatic ether, only HI (I
being strong nucleophile) can be used.
With hot concentrated H2SO4 : Secondary and tertiary ethers react with hot conc. H2SO4 to give
a mixture of alcohols and alkenes.
H SO
2 4 CH
CH3 3 C O CH 3
hot conc.
3 2 C CH 2 CH 3OH
Note : Ease of formation of alkene follows : 3 > 2 > 1 (with respect to alkyl group).
4. With Phosphorus pentachloride : Phosphorus pentachloride also brings about the cleavage of C – O
bond of ethers leading to the formation of alkyl halides.
5. Reaction with Acid chloride and Anhydrides : Acid chlorides and anhydrides react with ethers when
heated in the presence of anhydrous. ZnCl2 or AlCl3 to form alkyl halides and esters.
2 C H Clanhyd. ZnCl
Et O Et CH 3COCl 2 5 CH 3COOEt
Diethyl ether Acetyl chloride Ethyl chloride Ethyl acetate
6. Action of Air and Light : (Formation of Peroxides) : When exposed to air and light for a long time,
ethers are oxidised to form hydro-peroxides or simply peroxides.
light
Et O Et O 2
CH 3 C H O Et
Diethyl ether |
O O H
1 - Ethoxyethyl hydroperoxide
Therefore, serious explosions may occur during distillation of old samples of ethers if peroxides are not
removed. Presence of peroxides in old samples of ethers may be detected by shaking them with a freshly
prepared solution of FeSO4 followed by addition of KCNS. Appearance of a red colour indicates the
presence of peroxides. A simple method to remove peroxides is to shake an old sample of ether with
aqueous solution of KI or ferrous salt.
7. Hydrolysis of Ethers : Ethers when treated with dilute aqueous acids give alcohols.
3 H O
2 2 ROH H O
R O R
Oxirane (Epoxide)
Epoxides are cyclic ethers with three membered rings. In IUPAC system, epoxides are called as Oxiranes.
The most common epoxide is ethylene oxide.
Preparation of Oxiranes
1. Oxidation of Ethylene : Epoxide or ethylene oxide is prepared by partial oxidation of ethylene in
presence of Ag2O.
2. Epoxidation : The most important method of formation of epoxides is the reaction of an alkene with
an organic peroxy acid or peracid, such as perbenzoic acid (C6H5COOOH) or peracetic acid
(CH3COOOH) or mCPBA (m-chloroperoxobenzoic acid). This process is known as epoxidation.
Note : The above reaction is a stereo specific reaction i.e., it involves cis-addition of an electrophillic oxygen atom.
It means cis-alkene will give only cis-epoxide and a trans-alkene will give only trans-epoxide.
Reactions of Oxiranes
Due to the strain in the ring, epoxides are highly reactive towards nucleophillic substitution reaction
(unlike ethers). They undergo ring opening reactions so as to release the strain. Epoxides undergo acid
catalysed and base catalysed opening of the ring.
1. Acid Catalysed Opening : The acid reacts with epoxides to produce a protonated epoxide. The
protonated epoxide undergoes ring opening by attack of nucleophile (A–) on sterically hindered car-
bon atom, because acid catalysed ring opening is SN 1type reaction
2. Base Catalysed Opening : Epoxides can also undergo base-catalysed ring opening provided the
attacking nucleophile is also a strong base such as an alkoxide or hydroxide ion. A strong nucleophile
(alkoxide, RO) is able to open the ring by a backside attack (as observed in a SN2 reaction)
Note : Under acidic conditions, ring opening in protonated epoxide occurs to give a more stable (3)
carbonium ion.
Under basic conditions, the alkoxide simply attacks the less hindered carbon atom in an SN2 type
displacement.
Symmetrically substituted epoxides give the same product in both the acid-catalysed and base-catalysed
ring openings. An unsymmetrical epoxide gives different products under acid-catalysed and base-
catalysed conditions,
3. Cleavage of Oxiranes by Grignard Reagent and LiAlH4: In case of Grignard reagent, the Nu end, i.e.,
R attacks on the carbon atom of the epoxide. Here nucleophile attacks at less substituted ring carbon in the
base catalysed ring opening (As explained above).
Epoxides are reduced to alcohols an treatment with LiAlH4 ; hydride ion (as Nu–) is transferred to the less
crowded carbon.
(i)
Anisol undergoes bromination with Br2 in ethanoic acid, even in the absence of Iron (III) bromide
catalyst.
(iii) Nitration :
Dihydric alcohols are called as diols. There are two types of diols :
(i) Geminal diol (ii) Vicinal diol
Geminal diols are unstable because of steric reason. There are hydrates of carbonyl compounds.
The viccinal type of dihydric alcohols are called as Glycols (Di-ols). Some Important Glycols are given
below :
Preparations of Glycols
1. Hydroxylation of Alkenes
2. Hydrolysis of Halohydrins
HOCl aq
CH 3CH CH 2 CH 3 C H – C H 2 CH 3 – C H – C H 2
KOH
| | | |
OH Cl OH OH
(Halohydrins)
aq
4. Hydrolysis of Viccinal Dihalides C H 2 – C H 2 C H 2 – C H 2
KOH
| | | |
Br Br OH OH
Viccinal dihalides
CH 3 – CO
1. Mg
| CH 3 2 C C CH 3 2 (Pinnacol)
CH 3 2. H 2O
| |
OH OH
H H
| |
1.Mg
2 CH 3CHO CH 3 – C – C – CH 3
2.H 2 O
| |
OH OH
6. Reduction of Glyoxal(s)
Reactions of Glycol
1.
3. Polymerisation
Note : (i) Acetals are stable in alkaline medium and are not reduced. Hence keto groups are protected in acetal
forms. Acetals are very easily hydrolysed in acidic medium to give back aldehyde and ketones.
(ii) Aldehydes are more reactive than ketones in this reaction.
5. (a) Oxidation
4 HIO
CH 3 – C H – C H 2 CH 3 – CHO HCHO
| |
OH OH
Note : (i) ‘trans’ shows cleavage with resistance, whereas ‘cis’ shows cleavage instantly.
O
||
(ii) Special Case : In case when –CHOH and C groups are adjacent to each other, HIO4 also
breaks them as follows :
6. Intramolecular Condensation
CH 3 CH 3 CH 3
| | H 2SO 4
|
CH 3 – C – C – CH 3 CH 3 – C – C – CH 3
| | || |
OH OH O CH 3
(Pinnacol) (Pinnacolone)
Methyltert.butylAcetone
Mechanism :
Preparations of Glycerol
1. Saponification of oils/fats (glycerides)
2. Synthetic glycerol
Reactions of Glycerol
1. With conc. HNO3
3. Action of HI
If excess of glycerol of used.
If excess of HI is used.
CH 2 CH 3 CH 3 CH 3
|| | –I 2
| |
HI HI
C H C HI C H CH – I
| | || |
CH 2 I CH 2 I CH 2 CH 3
(Isopropy iodide)
4. Dehydration
CH 2OH CH 2
| KHSO
||
C HOH 4 C H (acrolein)
| |
CH 2OH CHO
Note : A mixture of glyceryl trinitrate and glycernyl dinitrate absorbed on kieselguhr (Porous earth) is dyna-
mite, an explosive.
Glycerol is used in the manufacture of polyster called glyptal, in medicines, cosmetics and in textile
processing.
Glycerol is miscible in water and is sweet in taste.
ILLUSTRATIONS Section - 5
Illustration - 1 An optically active alcohol A(C6H10O) absorbs two moles of hydrogen per mole of A upon
catalytic hydrogenation and gives a product B. The compound B is resistant to oxidation by CrO3 and does
not show any optical activity. Deduce the structures of A and B.
SOLUTION :
2 2H (O)
C6H10O (A) B resists oxidation
CrO3
(Optically active)
Illustration - 2 3, 3-Dimethylbutan-2-ol loses a molecule of water in the presence of hot conc. H2SO4 to
give tetramethyl ethylene as the major product. Suggest a proper mechanism. Also identify the minor product.
SOLUTION :
Illustration - 3 A compound of molecular formula C7H8O is insoluble in water and dil. Na2CO3 but dissolves
in dil. NaOH solution. On treatment with Br2 / H 2O, it readily gives a precipitate of C7H5OBr3. What is the
structure of compound ?
SOLUTION :
It can not be benzyl alcohol or anisole as alcohols and ether (o, p, m) are insoluble in NaOH. It can be only
be cresol. Note that phenols are soluble in dil. NaOH forming phenoxides.
Note that both – OH and – CH3 activate same positions (i.e. o and p). Though, due to sterie factor,
bromination at the position between OH and Me group is quite difficult.
Illustration - 4 A compound X(C5H8O) does not react appreciably with Lucas reagent at room temperature
but gives a precipitate with ammonical AgNO3. With excess of MeMgBr, 0.42 gm of X gives 224 mL of CH4
at STP. Treatment of X with H2 in presence of Pt catalyst followed by boiling with excess HI gives n-pentane.
Suggest the structure of X and give all reactions involved.
SOLUTION :
3 AgNO
X precipitate
X contains – C C – H group, which is confirmed by action of MeMgBr to give CH4.
0.42
mol of X 0.005 mol.
84
224
224 mL CH4 (STP) mol 0.01 mol of X
22400
1 mol X 2 mol CH4
Hence X contains two acidic H-atoms.
The structure of X should be : HC CH 2CH 2CH 2 OH
Note that ‘X’ has to be 1° alcohol as it does not give Lucas test. Also note that 2 alcohol react with Grignard
Reapent to give alkanes, hence Lucas test is very important here.
2 H HI
Finally checking : HC C CH 2CH 2CH 2OH H3C CH 2 CH 2CH 2CH3
Pt
(n Pentane)
Illustration - 5
SOLUTION :
Illustration - 6 Identify the products in the following reactions and comment on the stereochemistry of the
products.
(i) (ii)
SOLUTION :
(i) Observe that alcohol has a chiral centre.
Et Et Et
| Na
| _ CH3CH 2 Br
|
(A)
H C OH H C O Na H C O CH 2CH3
SN 2
| | |
Me Me Me
Note that here O – H bond breaks to give alkoxide and in SN2 reaction ether is formed retaining the
configuration of alcohol.
Et Et
| TsCl
|
H C OH H C OTs ;
| |
Me Me
HS will make an SN 2 attack from the back at carbon (chiral) to give an inverted configuration.
Note that TsO is a very good leaving group assisting SN 2 reaction.
(ii) Reaction of alcohol with SOCl2 proceed by intramolecular nucleophilie substitution reaction (SN i)
mechanism, hence there is retention in configuration.
Illustration - 7 Give the possible products in the following reactions. Also comment upon the type of
pathways.
2 4 ? ?? H SO
(a) CH 3CH 2OH CH 3CH 2CH 2OH
T ~ 140C
H SO
2 4 ? ??
(b) CH 3CH 2OH CH 3 3 C OH
T ~ 140C
SOLUTION :
2 4 H SO
(a) CH 3CH 2OH CH3CH 2CH 2OH
T ~140C
Note that both alcohols are 1 alcohols, so none of these is capable of carbocation formation (1 carbocations
being poorly stable). So here, ethers will be formed via SN2 pathway as temperature is around 140C.
In the first step, either or both of two alcohols can form oxonium ion (R O H 2 ) and then the second step, the
other one will make an SN2 attack on -carbon to give a protonated ether which eventually will give ether as
final product.
Hence the products (I, II, III) are formed via SN2 path.
H SO
2 4 ?
(b) CH3CH2OH CH3 C OH
3
Note that one of these is tertiary butyl alcohol (3), so it will form stable carbocation which will finally give
ether as the main product via SN1 path.
Note : A stable carbocation also give alkenes as minor product via E1 path.
H
CH3 3 C CH3 C CH 2
|
CH3 (E1)
(a) (b)
SOLUTION :
(a)
(b)
SOLUTION :
Note : Observe that Nu– (i.e., H2O18) attaches to more alkylated carbon in an acid catalysed ring opening.
It is SN 1type ring opening
O
O
| CH3 O H
|
CH3 C CH 2OCH3 CH 3 C CH 2OCH3 (C)
| |
CH3 CH3
Observe that Nu– (CH3O–) attaches to less alkylated carbon in a base catalysed ring opening.
CH3
| conc.
B: CH 3 C C H 2
| | H 2 SO4
18OH OH
SOLUTION :
conc. HI solvent in H2O
CH 3 CH3
| | _
H SN 1 I (Nu )
CH 3 C O CH3 CH3 C O CH3 CH3 C CH3OH CH 3 C I
3
| | | + (B) (A)
3°C ; stable
CH 3 CH 3 H
When solvent is ether, it being less polar favours SN2 path with I– as a strong nucleophile will make an SN2
attack at –CH3 group (no steric hindrance).
ph ph
| | H 2 SO4 conc. LiAlH 4 H 2 SO4 conc.
(a) ph C C Me A B C
170C
| |
OH OH
(b)
SOLUTION :
C6H5 CH3
| | conc.
(a) C6H 5 C C CH3 ? It is a case of Pinnacol-Pinnacolone type of rearrangement.
| | H 2SO 4
OH OH
Observe that first visualise the most stable carbocation and then follow migration in order : H ph R.
Rewriting (A) as :
(b)
+
Note : In general, R C O does not undergo rearrangement but if R is 3 then it breaks as mentioned below
:
For Example :
(c)
Illustration - 12 (a) How will you convert cyclohexanol to 1, 4-Dibromo-2-cyclohexene in not more than
4-steps ?
(b) How will you prepare 2, 3-Dimethyl-2-butanol from 2-Propanol as the only starting organic material ?
SOLUTION :
(a)
CH3 CH3
| |
(b) CH 3 C H CH3
CH3 C C H CH3
| |
OH OH
2, 3-Dimethyl-2-butanol
2 alcohol
3 alcohol
(Think of Grignard reagent)
CH3 CH3
PCl5 Mg / Et 2 O (CH3 ) 2 CO
| |
CH 3 C H CH 3 CH3 C H CH 3 CH3 C H CH 3 CH3 C C H CH3
| | | H 2O |
OH Cl MgCl OH
(a)
(b)
SOLUTION :
(a)
(b)
Observe carefully that this step will lead to nowhere as O H 2 is attached to phenyl ring. So think of alternative
path.
Illustration - 14
1. Br / H O
2 2 A
3 CH C CH .
3 C CH I HI ( conc.)
CH3CH CH 2
B DE
2. OH Na 0C
SOLUTION :
Note : I– as strong Nu– will atack at the least hindered CH3 group.
My Chapter Notes
Illustration - 1