Unit 7-10 – TB 2

C H E M I S T R Y
Theory Book
ORGANIC CHEMISTRY - 2

Alcohols

Reactions of alcohols
Reactions of alcohols can be classified into 4 types.

1. Nucleophilic substitution → Occurs by breaking the C − O bond'

2. Elimination reactions → Occurs by breaking the C − O bond.
3. Acidic reactions → Occurs by breaking the O − H bond.
4. Oxidation reactions

Nucleophilic substitution reactions of alcohols.

1. With PCl3 , PBr3 , PCl5

CH3 CH2 − OH + PCl3 CH3 CH2 − Cl + H3 PO3

CH3 CH2 − OH + PBr3 CH3 CH2 − Br + H3 PO3

CH3 CH2 − OH + PCl5 CH3 CH2 − Cl + POCl3

2. With HBr, HI

Alcohols undergo nucleophilic substitution reactions with HBr or HI producing the

corresponding Alkyl bromide or Alkyl iodide.

CH3 CH2 − OH + HBr CH3 CH2 − Br + H2 O

CH3 CH2 − OH + HI CH3 CH2 − I + H2 O

Mechanism -

▪ In the first step, in the presence of acids (HBr or HI) the -OH grouo converts into a a very good leaving group
(H2O) due to the the protonization of the O atom.
▪ This is a nucleophilic substitution reaction. During this reaction, the Brˉ ion acts as the nucleophile while
the leaving group is H2O.

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 ▪ Alcohols react with HCl only in the presence of Lewis acids. This fact is used when identifying primary,
secondary and tertiary alcohols in the Lucas reaction. ZnCl2 which is a lewis acid is used in the Licas
experiment as a catalyst.

Lucas reagent (HCl/ Anhydrous ZnCl2)

(HCl/ ZnCl2)
R − OH R − Cl

▪ Since the alkyl halide obtained by this reaction is insoluble in water as the reaction progresses the reaction
mixture tends to show a turbid nature. The time taken for the turbidity to form can be used to identify
primary, secondary and tertiary alcohols.
▪ Of the given reactons, the above nucleophilic substitution reaction takes place in two steps through an
intermediate carbocation. The rate of the reaction increases and the time taken for the turbidity
formation decreases when the stability of this intermediate carbocation increases.
▪ Therefore, tertiary alcohols give a turbidity in the presence of Lucas reagent in a very short time. Secondary
alcohols take a very long time to form the turbidity while primary alcohols react very slowly.

Elimination recations of alcohols.

In the presence of conc.sulphuric acid or alumina (Al2 O3 ) when heated to a high temperature alcohols
undergo elimination reactions. During these reactions, alcohols are dehydrated, and a water molecule is
removed from alcohols. The product of this is an alkene.

Acidic reactions of alcohols.

Na
R − CH2 − OH R − CH2 −O−Na+

Oxidation reactions of alcohols.

Alcohols can be oxidized by H+/KMnO4 or H+/K2Cr2O7 or H+/CrO3 . The product of oxidation depends on
whether the alcohol is primary, secondary or tertiary.

Oxidation of primary alcohols.

By the above mentioned oxidizing agents, primary alcohols are oxidized to form carboxylic acids through
the corresponding aldehydes.

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 When Pyridium chlorochromate (PCC) [C5H5NH]+[CrO3Cl]ˉ is used, the oxidation reaction stops at
aldehydes.

Oxidation of secondary alcohols.

Any of the above oxidants can be used to oxidize secondary alcohols producing ketones.

Oxidation of tertiary alcohols.

Usually tertiary alcohols do not undergo oxidation under the conditions which primary and secondary
alcohols do.
Phenol

▪ Special derivative of alcohol that is colourless or red in colour liquid in room temperature.
▪ High in acidity than alcohols. (Acidities will be discussed in detail)
Ex:

Reactions of phenol

 Phenols do not undergo nucleophilic substitution reactions by breaking the C − O bond, unlike alcohols.
Reasons for this are;
1. The strength of the C − O bond being greater than that of an ordinary alcohol. Two reasons;
i) Short, as the hybridization of C is sp2 .
ii) Based on resonace C − O being a partial double bond and not a single bond.

2. Phenyl cation being unstable. (C6 H5+ )

 The O − H group of phenol is a strong activating group and it is also an ortho-para director.

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 Due to the greater activity of phenol, benzene is highly reactive towards electrophilic reactions.
Accordingly, phenol shows electrophilic substitution reactions strongly. It is well explained by the
following examples.

1. Reaction between phenol and 𝐁𝐫𝟐

Benzene does not react with bromine. But phenol rapidly recats with bromine to produce 2, 4, 6–
tribromophenol. When this reaction is done in aqueous medium, (Br2 (aq)), the above obtained 2, 4, 6–
tribromophenol is observed as a white precipitate.

2. Nitration reaction of phenol

At 20 °C, phenol undergoes nitration with dilute acids. But, for the nitration of benzene, conc.
HNO3/ conc. H2SO4 and a high temperature is required. (50°C − 60°C).

 Due to the formation of complexes between freidal-craft catalysts (𝐀𝐥𝐂𝐥𝟑 ) and phenol, phenol cannot
be subjected to freidal-craft alkylation or acylation.

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 Aldehydes and Ketones

Introduction
Both aldehydes and ketons contain the functional carbonyl group (C = O) . Thhis functional group
of aldehydes is bonded to the hydrogen bond by one bond and to the alkyl or aryl (aromatic) group by the
other. However, the carbonyl group of the simplest aldehyde, formaldehyde (methanal) is bonded to two H
atoms. In ketones, the carbonyl group is bomded to alkyl or aryl groups on either sides.
The carbonyl carbon atom is sp2 hybridized and the three atoms attached to it lie on the same
plane (trigonal planar). The acrbon-oxygen double bond contains one 𝜎 bond and one 𝜋 bond.

The characteristic reaction of aldehydes and ketones is the nucleophilic addition reaction.

Nucleophilic addition reactions of aldehydes and ketones.

① Addition of 𝐇𝐂𝐍

This is done by adding a dilute crude acid into a mixture of the carbonyl compound and aqueous sodium
cyanide solution. Here the 𝐂𝐍ˉ ion acts as the nucleophile.

Mechanism -

② Reaction with Grignard reagent

In Grignard reagent the C– Mg bond is polarized as follows;

Hence, the R group of the Grignard reagent, acts as a nucleophile with carbonyl carbon by the electron
pairs of the R– Mg bond. The product of this would be the formation of an alkoxy magenisum halide.

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 By the hydrolysis of an alkoxy magnesium halide, the corresponding alcohol is formed. This is done by
an aqueous acid.

 During the reaction with Grignard, except for formaldehydes, all the other aldehydes give a
secondary alcohol while ketones give a tertiary alcohol. Formaldehyde produces a primary
alcohol.

 It is important to remember that preparation of the Grignard reagaent and reacting aldehydes with
ketones, is done under anhydrous conditions. Therefore, the reaction with Grignard reagent and the
hydrolysis of magenisum halides are two different steps.

③ Reaction with Ammonium and amines.

The reactions of amines with aldehydes and ketons are nucleophilic additions followed by an eleimination
reaction. The product formed her is called emine.

This reaction is corresponding to the reaction of aldehydes and ketones with 2,4 −
dinitrophenylhydrazine (Brady reagent)'

④ Reaction with 𝟐, 𝟒 − dinitrophenylhydrazine (𝟐, 𝟒 − 𝐃𝐍𝐏 or Brady reagent)

In this reaction, first the nucleophilic addition of 2,4-dinitrophenylhydrazine to the aldehyde or ketone
takes place. Then, one water molecule is removed such that the final product obtained is 2,4-
dinitrophenylhydrazone.
Accordingly, this reacyion mechanism is a nucleophilic addition followed by an eleimination
reaction.
The final product 2,4-dinitrophenylhydrazone is a dark yellow or orange coloured precipitate. Threfore,
this reaction is used in the identification of aldehydes and ketones.

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 As shown above this reaction consists of two steps, but, the product formed by the first step during
nucleophilic addition, which is, a hydroxy product cannot be separated under reaction conditions. Soon
as it id formed, it is dehydrated to form the final product.

⑤ Self-condensation of aldehydes and ketones.

Due to the strong ablility to attract electrons by the carbony group, the H atoms that are directly bonded
to the carbon atom of the carbonyl group (α − H) are acidic. These α – H can be removed as a proton
by bases (Eg : OH ‾). The carbanione shown here is stabilized by the resonance shown below.

The above carbanion acts as a nucleophile and attackes the carbon atom of the carbonyl group which is
not ionized. Therefore, aldehydes and ketones containing the α - hydrogen undergo base-catalyzed self-
condensation reactions.

Examples -

𝐢) Reactions of acetaldehyde in the presence of aqueous sodium hydroxide.

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 Overall reaction -

𝐢𝐢) Condensation of acetone in the presence of aqueous sodium hydroxide.

Overall reaction -

 When the addition products formed above are heated with acids they are easily dehydrated.

⑥ Reduction of aldehydes and ketones

𝐢) Using lithium aluminium hydride (𝐋𝐢𝐀𝐥𝐇𝟒) or sodium borohydride (𝐍𝐚𝐁𝐇𝟒)

By LiAlH4 or NaBH4 `aldehydes can be reduced to primary alcohols and ketones are reduced to secondary
alcohols. During these reducing reactions, hydride ions (H‾) are released by LiAlH4 or NaBH4. The hydride
ion acts as a nucleophile with the carbonyl carbon. Therefore, this reduction reaction can also be
considered as a nucleophilic addition reaction.

Due to high reactivity LiAlH4 , cannot be used in the presence of water and methanol.

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 𝐢𝐢) Reduction by Zn(Hg)/Conc. HCl (Clemmenson reduction)

During this reduction reaction the C = O group, is reduced to a methylene (CH2) group. Using this both
aldehydes and ketones can be converted to hydrocarbons.

⑦ Oxidation of aldehydes and ketons.

Since there is a H atom attached to the C = O group , Oxidants such as acidified potassium dichromate,
acidified chromic oxide, or acidified potassium permanganate, or mild oxidants like Tollen reagent or
Fehling’s solution can be used to easily oxidize aldehydes into carboxylic acids.

Since there are no H atoms bound to the C = O group in ketones, they do not easilt undergo oxidation.

𝐢) Oxidation by acidified 𝐊 𝟐 𝐂𝐫𝟐 𝐎𝟕 or acidified 𝐂𝐫𝐎𝟑 or acidified 𝐊𝐌𝐧𝐎𝟒 .

 In the presence of aldehyde the pink colour of the H+/KMnO4 solution turns colourless and the orange
colour of the H+/ Cr2O72- solution turns green. Using these reagents aldehydes and ketons can be
distinguished from each other.

𝐢𝐢) Oxidation by Tollen’s reagent. ([Ag(NH3)2]+) − Silver mirror test

Tollens reagent is a solution that contains Ag+ in the form of [Ag(NH3)2]+ . When aldehydes are oxidized
to carboxylic acids, the Ag+ ion oxidizes into metallic silver, and forms a silver irror within the test tube.
This silver mirror test is sued to identify aldehydes from ketones.

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 𝐢𝐢𝐢) Oxidation using Fehlings solution

Fehlings solution is a copper(II) tartrate solution in which aqueous sodium hydroxide is dissolved. This
is a dark blue coloured solution. When few drops of aldehyde is added to this olution and heated, the blue
colour gradually decreases and the brick-red colour cuprus oxide precipitate (copper (I) oxide)
precipitate is formed. Aldehydes and ketones can be distinguished by fehlings solution.

Chemistry of carboxylic acids

Introduction

Carboxylic acids are compounds that have C = O and OH group and carries the carboxylic group (COOH).
Usually carboxylic acids are more acidic than other compounds with the OH group. But they are less acidic
than common mineral acids.

Reactions of carboxylic acids.

3 forms of reactions;

(1) Reactions related to the breaking of the 𝐎– 𝐇 bond

Caboxylic acids are acidid. The react with alkali metals such as sodium and potassium, alikales
(strong bases) such as NaOH and KOH, and weak acids such as Na2CO3 and NaHCO3 '

(2) Reactions related to the breaking of the 𝐂– 𝐎 bond

(a) Reactionwith PCl3 or PCl5

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 (b) Reaction with alcohols (Esterification)

In the presence of acid catalayst, carboxylic acids react with alcohols and form esters.

Eventhough the above reaction can be seen as a simple nucleophilic substitution reaction where
the −OH group is replaced by the −OC2H5 group, here the first step is, C2H5OH molecule is added
as a nucleophile through C=O and forms a tetrahedral intermediate. Under the acidic
conditions that the reaction is taken place a water molecule is removed from the
intermediate and the ester is formed.

(3) Reduction of carboxylic acids by LiAlH4

Carboxylic acids react with LiAlH4 which is a strong reductant and form primary alcohols. Carboxylic
acids are not reduced by NaBH4 which is a less powerful reductant than LiAlH4.

Reactions of the derivatives of carboxylic acids.

Reactions of acid chlorides.

① Reaction with aqueous sodium hydroxide.

Acid chlorides react with aqueous sodium hydroxide while producing the corresponding carboxylic acid.
This carboxylic acid can be reacted with excess NaOH to form its sodium salt.

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 Mechanism -

In the above reaction, OH‾ is the nucleophile whie Cl‾ is the leaving group.

② Reaction with water

By a very similar mechanism acid chlorides react with water and form the corresponding carboxylic
acids.

③ Reaction with alcohol and phenol. (Esterification)

Acid chlorides react with alcohols and phenols to form alkyl ester and phenyl ester respectively.

④ Reactions with ammonis and primary amines.

Acid chlored react with ammonia producing primary amides.

Acid chlorides react with primary amines producing secomdary amides.

Note – The amides that have two H atoms attached to the N atom is considered as a primary amide.
When it has one H atom replaced by an alkyl group it is considered as a secondary amide. When the
H atoms are both replaced by two alkyl groups they are called tertiary amides.

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 Reactions of Esters

① Reactions with dilute mineral acids.

Esters react with dilute acids and produce the corresponding carboxylic acid and the alcohol. During this
reaction water acts as the nucleophile and ester undergoes hydrolysis. This reaction too takes place
through a tetrahedral intermediate similar to that formed during the formation of esters.

② Reactions with aqueous sodium hydroxide.

When recated with aqueous sodium hydroxide easter produces the corresponding salt of carboxylic acid
and the alcohol. The mechanism of this reaction is similar to that of acid chlorides with NaOH.

③ Reactions with Grignard reagent

Ester react with Grignard reagent to give a tertiary alcohol. During this reaction, ester is first converted to
a ketone and the ketone rapidly reats with Grignard reagent and gives tertiary alcohol as the product.

Note : Since ketones reacts with Grignard reagent very rapidly, the reaction cannot be stopped at
the ketone formation stage.

④ Oxidation by LiAlH4

LiAlH4, oxidizes esters into alcohols.

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 Raections of Amides

① Reaction with aqueous sodium hydroxide.

When amides are heated with aqueous NaOH solution, ammonia gas is released and the salt of the
corresponding carboxylic acid is formed.

② Reduction using LiAlH4

Amides can be converted into the corresponding amines by LiAlH4.

Naitrogenous organic compounds

There are two main types of nitrogenous organic compounds.

1. Amine
2. Amide – discussed below under carboxylic acid derivatives.

Chmeistry of Amines
Introduction

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 Reactions of primary amines

Given that N has a lone pair electron, amines can act as a nucleophile. Given below is are the reactions of
amines with different reactants, whener amines act as the nucleophile.

① Reactions of amines with alkyl halides.

Primary amines react with alkyl halides and produce secondary amines.

In these secondary amines too N has lone pair electrons. They further react with alkyl halides and form
tertiary amines. Tertiary amines too have lone pair electrons and therefore they further react with alkyl
halides to form quaternary ammonium salt.

② Reactions of amines with acid halides.

Acid chlorides react with primary amines to produce secondary amide.

③ Reactions of aldehydes and ketones with amines.

This reaction consisist of a nucleophilic addition followed by an elimination reaction.The product formed
here is called emine.

④ Reactions of Amines with nitrous acid. (NaNO2/ HCl) w;r m%;sls%hdj

Primary amines react with nitrous acid to produce diazonium salt. Alkyl diazonium salt is unstable
therefore they react rapidly evolving nitrogen gas and convert into alcohol.

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 Aromatic diazonium salts formed fom aromatic amines are more stable than alkyldiazonium salts.
Therefore, under low temparatures, solutions of the aromatic diazonium salts can be obtained.

Aniline

The simplest aromatic amine. Here, NH2 group is bounded to the benzene ring.

The reaction fo the benzene ring of aniline

Since the NH2 grop strongly activates the benzene ring towards electrophilic substitution reactions,
similar to phenol, even aniline reacts with bromine and produces 2,4,6 – 𝑡𝑟𝑖𝑏𝑟𝑜𝑚𝑜𝑎𝑛𝑖𝑙𝑖𝑛𝑒.

When this reaction is taken place with bromine water, 2, 4, 6 − 𝑡𝑟𝑖𝑏𝑟𝑜𝑚𝑜𝑎𝑛𝑖𝑙𝑖𝑛𝑒 is observed as a white
precipitate.
Reactions of aromatic diazonium salts.

Aromatic amines such as aniline when reacted with nitrogen acids (NaNO2/ HCl) aromatic diazonium salt
is formed. They decompose in room temperature to give phenols. Aromatic diazonium salts are stable
than aliphatic diazonium salts. Therefore, under low temperatures when this reaction takes place, the
conversion of the aromatic diazonium salt into phenol can be reduced and thereby separate the diazonium
salt.

Hence, aromatic diazonium salts are prepared at low temperatures (𝟎 – 𝟓 °𝐂) by treating primary
amines with an aqueous 𝐍𝐚𝐍𝐎𝟐 solution in the presence of a dilute acid 𝐇𝐂𝐥 or 𝐇𝟐𝐒𝐎𝟒 . Under these
temperatures too diazonium salts are decomposed slowly. Therefore, soon after the preparation they are
used for the necessary reaction.

Diazonium salts undergo several reactions. They can be divided into two;

1. Reactions where the diazonium group can be replaced by another atom or group.
2. Reactions where the diazonium ion reacts as an eletrophile and produces a nitrogen containing
compound.

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 wñ, oikdhl
Cl
CuCl/HCl + N2 ↑

+ N2 ↑
Br

| wdidfjka bf.k.kak
CuBr/HBr
+ N2 ↑

H3 PO2
I
KI
+ N2 ↑
∆
NH2
NaNO2 /HCl N + ≡ NCl−
5℃
CN
CuCN/HCN
+ N2 ↑

OH
H2 O
N=N OH
NaOH ;eô,s meye;s vhs
OH H
OH N=N
+ N2 ↑ OH
NaOH r;= meye;s vhs

17
 1. Reactions where another group or atom replaces the diazonium group

① Reaction between salt and diazonium salt

When aqueous solutions of diazonium salts are heated, phenol is formed.

② Reaction between diazonium salt and hypophosphorous acid. (𝐇𝟑𝐏𝐎𝟐)

When diazonium salr, is treated with the hypophosphorous acid the diazonium group is replaced by a H
atom.

③ Reaction between diazonium salt and CuCl and CuBr.

When diazonium salts are reacted with CuCl or CuBr, the corresponding aromatic halides are formed.
Copper powder can be used instead of copper(I) and hydrogen halides also can be used for this reaction.
(Cu/HCl or HBr).

④ Reaction between diazonium salt and CuCN.

When diazonium salts are reacted with CuCN, the diazonium group is replaced by CN group.

⑤ Reaction between diazonium salt and KI.

When diazonium salt is reacted with KI, the diazonium group is replaced by I.

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 2. Reactions where the diazonium ion acts as an electrophile and produces nitrogen
containing product.

Since N has a positive charge, aryldiazonium ions can acts as electrophiles. Under alkaline conditions they
react with phenol. Benzene diazonium chloride reacts with phenol in the presence of aqueous NaOH while
giving an orange coloured solution and reacts with β − naphthol (2-napthol) giving a rad coloured
compound.

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