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Chapter
23
General Organic Chemistry
sp sp 2
Hybridisation in Organic Compounds sp 2
(1) The process of mixing atomic orbitals to form a set of new (iii) CH 3 CH CH CH 2 C N
equivalent orbitals is termed as hybridisation. There are three types of
hybridisation, sp 3 sp 2 sp 2 sp 3 sp sp
(i) sp 3 hybridisation (involved in saturated organic compounds
containing only single covalent bonds), (iv) HC C CH CH 2
2
(ii) sp hybridisation (involved in organic compounds having sp sp sp 2 sp 2
carbon atoms linked by double bonds) and
(iii) sp hybridisation (involved in organic compounds having In diamond carbon is sp hybridised and in graphite carbon is
3
s sp sp 2 sp 3 p
% s - character and electronegativityin decreasing order.
(iii) Bond length variation in hydrocarbons
Number of lp’s can be determined as follows,
(a) If carbon has - bonds or positive charge or odd electron, than % of s orbital character
lp on carbon will be zero. 1 1
(b) If carbon has negative charge, then lp will be equal to one.
C C bond length C H bond length
Number of electron pairs (ep) tells us the type of hybridisation as
follows, Table : 23.2
Thus, acidic nature is, In gas phase or in aqueous solvents such as chlorobenzene etc,
the solvation effect, i.e., the stabilization of the conjugate acid due to H -
CCl 3 COOH CHCl 2 COOH CH 2 ClCOOH CH 3 COOH bonding are absent and hence in these media the basicity of amines
Trichloro Dichloro Monochloro Aceticacid
acetic acid acetic acid acetic acid depends only on the +I effect of the alkyl group thus the basicity of amines
(c) Strength of aliphatic carboxylic acids and benzoic acid (vii) Basicity of alcohols : The decreasing order of base strength in
alcohols is due to +I effect of alkyl groups.
R COOH C6 H 5 COOH
(CH 3 )3 COH (CH 3 )2 CHOH CH 3 CH 2 OH CH 3 OH
I group I group (3 o ) (2 o ) (1 o )
(viii) Stability of carbonium ion :+I effect tends to decrease the (+ve)
charge and –I effect tends to increases the +ve charge on carbocation.
Hence benzoic acid is stronger acid than aliphatic carboxylic acids
but exception is formic acid. Thus, (CH 3 )3 C (CH 3 )2 CH CH 3 CH 2 CH 3
HCOOH > C 6 H 5 COOH > RCOOH
(ix) Stability of carbanion : Stability of carbanion increases with
Acid strength in decreasing order increasing – I effect.
Decreasing order of acids :
CH 3 CH 3 CH 2 (CH 3 )2 CH (CH 3 )3 C
NO 2CH 2COOH FCH2COOH ClCH 2COOH BrCH2COOH .
Resonance effect or mesomeric effect
F3C COOH Cl3C COOH Br3C COOH I3C COOH .
(1) The effect in which electrons are transferred from a multiple
CH 3 OH CH 3 CH 2 OH (CH 3 ) 2 CHOH (CH 3 )3 COH bond to an atom, or from a multiple bond to a single covalent bond or lone
Methyl Ethyl Iso propyl Tert butyl pair (s) of electrons from an atom to the adjacent single covalent bond is
alcohol Alcohol alcohol alcohol called mesomeric effect or simply as M-effect. In case of the compound with
As compared to water, phenol is more acidic (–I effect) but methyl conjugated system of double bonds, the mesomeric effect is transmitted
through whole of the conjugated system and thus the effect may better be
alcohol is less acidic (+I effect).
known as conjugative effect.
OH H OH > CH 3 OH (2) Groups which have the capacity to increase the electron density
Phenol Water Methyl alcohol
of the rest of the molecule are said to have M effect. Such groups
(vi) Relative strength of the bases (Basic nature of NH 2 ) possess lone pairs of electrons. Groups which decrease the electron density
of the rest of the molecule by withdrawing electron pairs are said to have
The difference in base strength in various amines can be explained
M effect, e.g.,
on the basis of inductive effect. The +I effect increases the electron density
(a) The groups which donate electrons to the double bond or to a
while –I effect decreases it. The amines are stronger bases than NH 3 as
conjugated system are said to have M effect or R effect.
the alkyl groups increase electron density on nitrogen due to + I effect while
ClNH 2 is less basic due to –I effect. “So more is the tendency to donate M effect groups :
electron pair for coordination with proton, the more is basic nature, i.e., .. ..
more is the negative charge on nitrogen atom (due to +I effect of alkyl Cl, Br, I, N H 2 , NR 2 ,OH ,OR,SH ,OCH 3 , S R
group), the more is basic nature”. ..
Thus, the basic nature decreases in the order; (b) The groups which withdraw electrons from the double bond or
from a conjugated system towards itself due to resonance are said to have
(C 2 H 5 )2 NH CH 3 CH 2 NH 2 CH 3 NH 2 NH 3 ClNH 2
Diethyl Ethyl Methyl Ammonia Chloro M effect or R effect.
amine amine amine amine
M effect groups :
The order of basicity is as given below;
O
Alkyl groups (R– ) Relative base strength ||
R2 NH RNH 2 R3 N NH 3 NO 2 ,C N , C ,CHO ,COOH ,SO 3 H
CH 3
1018 General Organic Chemistry
(3) The inductive and mesomeric effects, when present together, (iv) Resonating structures due to hyperconjugation may be written
may act in the same direction or oppose each other. The mesomeric effect is involving “no bond” between the alpha carbon and hydrogen atoms.
more powerful than the former. For example, in vinyl chloride due to – I
effect the chlorine atom should develop a negative charge but on account of
H H
mesomeric effect it has positive charge. |
H C CH CH 2 H C CH C H 2
.. .. | |
: Cl CH CH 2 : Cl CH CH 2 H H
.. ..
H H
Application of mesomeric effect : It explains, | |
(1) Low reactivity of aryl and vinyl halides, H C CH C H 2 H C CH C H 2
|
(2) The acidic nature of carboxylic acids, H H
(3) Basic character comparison of ethylamine and aniline,
(4) The stability of some free radicals, carbocations and carbanions. (v) Number of resonating structures due to the hyperconjugation =
Number of -hydrogens + 1.
Difference between Resonance and Mesomerism : Although both
resonance and mesomerism represent the same phenomenon, they differ in Applications of hyperconjugation
the following respect : Resonance involves all types of electron (1) Stability of alkenes : Hyperconjugation explains the stability of
displacements while mesomerism is noticeable only in those cases where a certain alkenes over other alkenes.
multiple bond is in conjugation with a multiple bond or lone pair of
Stability of alkenes Number of alpha hydrogens Number of
electron.
resonating structures
Example :
CH 3 CH CH 2 CH 3 CH 2 CH CH 2 CH 3 CH CH CH 2
|
.. CH 3
(i) H 2 C CH CH CH 2 H 2 C CH CH C H 2 Stability in decreasing order
Cl Cl
| | C O CN C O
Cl C CH CH 2 Cl C CH C H
2
|
| CN
Cl Cl
The attacking reagent is not attached to that atom on which
electrons have been transferred.
The meta directing influence and the deactivating effect of CX 3
(3) Direction of the shift of electron pair : The direction of the shift
group in electrophilic aromatic substitution reaction can be explained by of electron pair can be decided on the basis of following points.
this effect.
(i) When the groups linked to a multiple bond are similar, the shift
X X X X can occur in either direction.
| | | |
X C X X C X X C X X C X (ii) When the dissimilar groups are linked on the two ends of the
| || || || double bond, the shift is decided by the direction of inductive effect.
+
In the case of carbonyl group, the shift is always towards oxygen,
i.e., more electronegative atom.
Inductomeric effect C O C O :
Inductomeric effect is the temporary effect which enhances the In cases where inductive effect and electromeric effect
inductive effect and it accounts only in the presence of an attacking reagent. simultaneously operate, usually electrometric effect predominates.
Example,
H Cleavage (fission or breaking) of covalent bonds
H Breaking of covalent bond of the compound is known as bond
HO H C Cl HO....... ..... C..... ....... Cl fission. A bond can be broken by two ways,
H (1) Homolytic bond fission or Homolysis
H H (i) In homolysis, the covalent bond is broken in such a way that
H each resulting species gets its own electron. This leads to the formation of
Cl odd electron species known as free radical.
HO C H
H . .
A : B A B
In methyl chloride the –I effect of Cl group is further increased Free radical
temporarily by the approach of hydroxyl ion.
1020 General Organic Chemistry
(ii) The factor which favours homolysis is that the difference in is termed as carbocation. If negative charge is present on the carbon then
electronegativity between A and B is less or zero. anion is termed as carbanion.
(iii) Homolysis takes place in gaseous phase or in the presence of (ii) The factor which favours heterolysis is greater difference of
non polar solvents (CCl 4 , CS 2 ) , peroxide, UV light, heat ( 500 o C) , electronegativities between A and B .
electricity and free radical. (iii) Mechanism of the reaction in which heterolysis takes place is
(iv) Mechanism of the reaction in which homolysis takes place is known as heterolytic mechanism or ionic mechanism.
known as homolytic mechanism or free radical mechanism. (iv) The energy required for heterolysis is always greater than that
(2) Heterolytic bond fission or heterolysis for homolysis due to electrostatic forces of attraction between ions.
(i) In heterolysis, the covalent bond is broken in such a way that Reaction Intermediates
one species (i.e., less electronegative) is deprived of its own electron, while
the other species gains both the electrons. Short lived fragments called reaction intermediates result from
homolytic and heterolytic bond fission. The important reaction
intermediates are free radicals, carbocations, carbanions, carbenes, benzyne
A : B A: B and nitrenes.
carbanion carbocation
Benzyne (ii) It reacts with strong nucleophile like NH 2
(1) 1, 2-Didehydrobenzene, C6 H 4 and its derivatives are called NH
NH
H
2
2
the ring ..
R – .N. These two are lone pair of electrons
(3) Benzyne intermediate is aromatic in character.
(4) When halobenzene is heated with sodamide formation of These two may be paired or unpaired
benzyne takes place. (3) In general nitrenes obey Hunds rule and the ground state triplet
Cl with two degenerate sp -orbitals containing a single electron each.
NaNH 2
R–N
(5) (i) It behaves as dienophile and gives Diels-Alder reaction with sp-Triplet nitrene
diene. (4) Nitrenes can be generated, in situ, by the following methods,
General Organic Chemistry 1021
(i) By action of Br2 in presence of a base on a 1 o amide (2) Nucleophiles : Electron rich species or electron donors are called
nucleophiles. Nucleophiles can be classified into three categories :
(Hofmann-bromamide reaction),
(i) Charged nucleophiles : Negatively charged species are called
O O O charged nucleophiles.
|| ||
|| . .
R C NH 2 2 R C NHBr R C N Br
Br / NaOH OH
1 o Amide H 2O .. H , O H , R O, C H 3 , X , S H , R S
(ii) Neutral nucleophiles : It can be classified into two categories :
(a) Neutral covalent compound, in which central atom has complete
O octet, has at least one lone pair of electrons and all atoms present on
|| . . central atom should not be electronegative, is neutral nucleophile.
R C N O C N R
Rearrangem ent
Br . . Isocyanate .. .. .. .. .. ..
N H 3, R N H 2 , R2 N H , R3 N , N H 2 N H 2 (Nitrogen nucleophile)
KOH
R NH 2 K 2 CO 3
(Hydrolysis) 1 o Amine .. .. ..
H O H , R O H , R O R (Oxygen nucleophiles)
(ii) By decomposition of azides in presence of heat or light. .. .. ..
.. .. .. .. .. ..
or h ν
R N N N : R N : N N H S H , R S H , R S R (Sulphur nucleophiles)
Alkylazide Alkylnitrene .. .. ..
.. .. .. .. ..
(iii) Unsubstituted nitrene (H N :) can be obtained by photolysis P H 3 , R P H 2 , R 2 P H , R3 P (Phosphorus nucleophiles)
of (or by passing electric discharge through) NH 3 , N 2 H 4 or N 3 H . (b) Organic compound containing carbon, carbon multiple bond/
bonds behaves as nucleophile.
Attacking reagents
Alkenes, Alkynes, Benzene,
The fission of the substrate molecule to create centres of high or
low electron density is influenced by attacking reagents. Most of the CH 2 CH CH CH 2 , CH 2 CH C CH
attacking reagents can be classified into two main groups. (iii) Ambident nucleophiles : Species having two nucleophilic
Electrophiles or electrophilic reagents and Nucleophiles or centres out of which, one is neutral (complete octet and has at least one
nucleophilic reagents. lone pair of electrons) and the other is charged (negative charge) behaves as
(1) Electrophiles : Electron deficient species or electron acceptor is ambident nucleophile
an electrophile.
O
It can be classified into two categories : .. ..
(i) Charged electrophiles : Positively charged species in which C N , O N O, O S OH
central atom has incomplete octet is called charged electrophile.
O
O
H , X , R, N , N O, S O3 H Organometallic compounds are nucleophiles.
O .. Nucleophiles are Lewis bases.
All cations are charged electrophiles except cations of IA, IIA group Organic compounds which behave as an electrophile as well as a
nucleophile : Organic compound in which carbon is bonded with
elements, Al and NH 4 electronegative atom (O, N, S) by multiple bond/bonds behaves as
(ii) Neutral electrophiles : It can be classified into three categories, electrophile as well as nucleophile :
(a) Neutral covalent compound in which central atom has O O O O
|| || || ||
incomplete octet is neutral electrophile,
R C H , R C R, R C OH , R C Cl ,
. .. ..
BeCl 2 , BH 3 , ZnCl 2 , AlX3, FeX 3 , CH 3 , CH 2 , CX 2 O O
|| ||
(b) Neutral covalent compound in which central atom has complete R C OR, R C NH 2 , R C N , R N C
or expended octet and central atom has unfilled –d-sub-shell is neutral During the course of chemical reaction electrophile reacts with
electrophile,
nucleophile.
SnCl 4 , SiCl4 , PCl5 , SF6 , IF7 Strong Lewis acid is stronger electrophile
(c) Neutral covalent compound in which central atom is bonded
only with two or more than two electronegative atoms is called neutral CO 2 N O 2 S O 3 H . Stronger is an acid, weaker is its conjugated
electrophile. base or weaker is the nucleophile.
BeCl 2 , BX 3 , AlX3 , FeX 3 , SnCl 4 , PCl3 ; Examples : HF H 2 O NH 3 CH 4
..
PCl5 , NF3 , C X 2 , CO 2 , SO 3 , CS 2 , F OH NH 2 CH 3
Increasing order of nucleophilicity.
Cl 2 , Br2 and I2 also behave as neutral electrophiles.
Electrophiles are Lewis acids. Types of organic reactions
1022 General Organic Chemistry
It is convenient to classify the numerous reactions of the various (iii) The leaving power of some nucleophilic groups are given below
classes of organic compound into four types, in decreasing order,
Substitution reactions, Addition reaction, O
O O
Elimination reactions, Rearrangement reactions, || || ||
CF3 S O Br S O CH 3 SO
Substitution reactions || || ||
Replacement of an atom or group of the substrate by any other O O O
atom or group is known as substitution reactions. O O
Substituting or || ||
Examples : attacking group C 6 H 5 S O CH 3 S O
Leaving group
|| ||
O O
CH 3 CH 2 Br NaOH CH 3 CH 2 OH NaBr O O
Ethyl bromide Ethyl alcohol
|| ||
(Bromine atom is replaced by hydroxyl group) I Br CF3 C O H O Cl F CH 3 C O
(iv) In these reactions leaving group of the substrate is replaced by
Types of substitution reactions : On the basis of the nature of another nucleophile. If reagent is neutral then leaving group is replaced by
attacking species substitution reactions are classified into following three negative part of the reagent. Negative part of the reagent is always
categories, nucleophilic in character.
(1) Nucleophilic substitution reactions E Nu
R L R Nu L ; R L Nu R Nu L
(2) Electrophilic substitution reactions (v) In S N reactions basicity of leaving group should be less than
(3) Free radical substitution reactions the basicity of incoming nucleophilic group. Thus strongly basic nucleophilic
(1) Nucleophilic substitution reactions group replaces weakly basic nucleophilic group of the substrate.
(i) Many substitution reactions, especially at the saturated carbon Example : R Cl
OH
R OH Cl .....(A)
( NaOH )
atom in aliphatic compounds such as alkyl halides, are brought about by
nucleophilic reagents or nucleophiles. Basicity of OH is more than Cl hence OH replaces Cl as Cl .
R X OH R OH X R OH R Cl OH ......(B)
Cl
Substrate Nucleophile Leaving group
( HCl )
Factors S 2 Reactions
N
S 1 Reactions
N
Number of steps
R : L R : L
Slow
One: R : L : Nu R : Nu : L Two: (i)
(ii) R : Nu R : Nu
Fast
predominates.
Stereochemistry Complete inversion of configuration takes place. Inversion and retention takes place.
Reactivity order of alkyl halides Methyl>1°>2°>3°halides. (I Br Cl F) 3°>2°>1° > methyl halides. (I Br Cl F)
Rearrangement No rearranged product is formed (except for Rearranged products can be formed.
allylic).
Nature of nucleophiles Favoured by strong and high concentration of Favoured by mild and low concentration of nucleophiles.
nucleophiles.
Polarity Favoured by solvents of low polarity. Favoured by solvents of high polarity.
Reaction rate determining factor By steric hindrance.
By electronic factor (stability of R ).
Catalysis Not catalysed by any catalyst (phase transfer). Catalysed by Lewis and Bronsted acids, e.g.,
Ag, AlCl3 , ZnCl 2 and strong HA.
(2) Electrophilic substitutions reactions : Electrophilic substitution written as S E1 (unimolecular)and if the order is 2, it is S E 2
involves the attack by an electrophile. It is represented as S (S stands for
E
(Bimolecular).
substitution and E stands for elctrophile). If the order of reaction is 1, it is
S 1 Reaction mechanism : Electrophilic substitution in aliphatic compounds are very S 2 Reaction mechanism : Electrophilic substitution is very
E E
rare; some of the important examples are: common in benzene nucleus (aromatic compounds) in which -
(i) Replacement of the metal atom in an organometallic compound by hydrogen : electrons are highly delocalized and an electrophile can attack this
region of high electron density.
RM H RH M In all electrophilic aromatic substitution reactions, it involves:
MgBr H Step 1. The formation of an electrophile, E, i.e.,
e.g., CH 3 CH 2 MgBr CH 3 CH 2 CH 3 CH 3
In halogenation; Cl Cl FeCl3 Cl Fe Cl 4
CH 3 CH 2 MgBr H Br CH 3 CH 2
H
CH 3 CH 3 MgBr2
CH 3 CH 2 Na C6 H6 CH 3 CH 3 C6 H5 Na In nitration; HNO 3 2 H 2 SO 4 NO 2 2 HSO 4 H 3 O
(ii) Decarboxylation of silver salt of carboxylic acid by means of bromine: In sulphonation; 2 H 2 SO 4 SO 3 HSO 4 H 3 O
R3 C C OAg Br Br R3 C C O Br Br Ag In Friedel-crafts reaction; R Cl AlCl3 R AlCl4
|| ||
O O RCOCl AlCl3 RCO AlCl4
R3C Br CO 2 AgBr
Step 2. The electrophile attacks the aromatic ring to form
(iii) Isotopic exchange of hydrogen for deuterium or tritium: carbonium ion (or arenium ion) which is stabilized by resonance.
H E H E H E
RH D⇋ RDH
E
R H T ⇋ R T H Benzene +
(3) Free radical substitution reactions : Free radical substitution CH 4 Cl 2 CH 3 Cl HCl
UV
reactions involves the attack by a free radical. These reactions occurs by free Methane light Methyl chloride
radical mechanism which involves Initiation, Propagation and Termination
steps. Examples, (ii) Arylation of aromatic compounds (Gomberg reaction) : The
(i) Chlorination of methane : The chlorination of methane in the reaction of benzene diazonium halide with benzene gives diphenyl by a free
presence of ultraviolet light is an examples of free radical substitution. radical substitution reaction.
1024 General Organic Chemistry
C6 H 5 H C6 H 5 N 2 X C6 H 5 C6 H 5
Alkali
N 2 HX CH 3
Benzene diazonium halide Diphenyl
CH 3 CH CH 2 , C CH 2 ,
(iii) Wurtz reaction : Ethyl bromide on treatment with metallic CH 3
sodium forms butane, ethane and ethylene by involving free radical
C6 H 5
mechanism.
C CH C 6 H 5 , C6 H 5 CH CH 2
(iv) Allylic bromination by NBS (N-Bromosuccinimide) : NBS is a
C6 H 5
selective brominating agent and it normally brominates the ethylenic
compounds in the allylic (CH 2 CH CH 2 ) position. This type of Following alkenes will not give addition reaction according to
Markownikoff’s rule.
reaction involving substitution at the alpha carbon atom with respect to the
double bond is termed Allylic substitution. It is also used for benzylic R R
bromination. Some examples are: CH 2 CH 2 , R CH CH R, C C ,
CH 2 CO R R
CH 3 CH CH 2 N Br
CCl 4
C6 H 5 C6 H 5
Propene
CH 2 CO CC
NBS
C6 H 5 C6 H 5
CH 2 CO (vi) Unsymmetrical alkenes having the following general structure
Br CH 2 CH CH 2 NH give addition according to anti Markownikoff’s rule.
Allylbromide
CH 2 CO CH 2 CH G , where G is a strong –I group such as
Succinimide
Addition reactions O
||
These reactions are given by those compounds which have at least CX 3 , NO 2, CN ,CHO ,COR ,COOH , C Z
one bond,
(Z Cl, OH, OR, NH 2 )
O
|| Example:
i.e., ( C C ,C C , C , C N ). In such reaction there
Cl
is loss of one bond and gain of two bonds. Thus product of the |
reaction is generally more stable than the reactant. The reaction is a CH 2 CH CHO HCl
CH 2 CH 2 CHO
Anti- Markowniko ff's addition
spontaneous reaction.
(vii) Mechanism of electrophilic addition reactions is as follows,
Types of addition reactions : Addition reactions can be classified
|
into three categories on the basis of the nature of initiating species. CC E
Slow
C C E
Olefin Electrophile |
(1) Electrophilic additions Carbonium ion
(2) Nucleophilic additions | |
Nucleophilic addition (A ) reactions on carbonyl compounds will be (1) Types of - elimination reactions : In analogy with substitution
reactions, - elimination reactions are divided into three types:
N
in order:
H H3C H 3C (i) E (Elimination unimolecular) reaction, (ii) E (Elimination
1 2
reaction
H H H 3C
(i) E (Elimination unimolecular) reaction : Consider the following
Decreasing order of nucleophilic addition in some species. 1
reaction,
O O
|| || CH 3
C 6 H 5 CH 2 COCH 3 CH 3 COCH 3 C 6 H 5 C CH 3 C 6 H 5 C C 6 H 5 CHO CH 3
| C H O/
CH 3 C Cl 25 CH C C 2 H 5 OH Cl
COCH 3 COCl COOCH 3 CONH 2 COOH |
2
CH 3 CH 3
(3) Free radical addition reactions : Those reactions which involve
the initial attack by a free radical are known as free radical reactions. (a) Reaction velocity depends only on the concentration of the
Addition of hydrogen bromide to alkenes (say, propylene) in the presence of substrate; thus reaction is unimolecular reaction.
peroxide (radical initiator) follows free radical mechanism. Free radical
Rate [Substrate]
reactions generally take place in non-polar solvents such as CCl 4 , high
temperature, in presence of light or a free radical producing substance like (b) Product formation takes place by the formation of carbocation
as reaction intermediate (RI).
O 2 and peroxides.
(c) Since reaction intermediate is carbocation, rearrangement is
Elimination reactions possible in E reaction.
1
Elimination reactions are formally the reverse of addition reactions (d) Reaction is carried out in the presence of polar protic solvent.
and involve the removal of the two groups (Generally, one being a proton)
from one or two carbon atoms of a molecule to form an unsaturated (e) The E reaction occurs in two steps,
1
Step 2.
1026 General Organic Chemistry
rule.
..
B H CH 2 C CH 3 B - - - - H - - - -CH 2 - - - - C CH 3
| | In E reactions, product formation always takes place by
CH 3 CH 3 1cb
Hofmann rule.
TS 2
In E reactions, product formation takes place by Saytzeff as well
2
CH 3
as Hofmann rule. In almost all E reactions product formation take place by
2
B H CH 2 C
fast
Saytzeff rule.
CH 3
(ii) E (Elimination bimolecular) reaction : Consider the following
2
(3) Examples of - elimination reactions
reaction, (i) Dehydrohalogenation is removal of HX from alkyl halides with
alcoholic KOH or KNH 2 or ter- BuOK (Potassium tertiary butoxide) and
CH 3 CH 2 CH 2 Br CH 3 CH CH 2 H Br
Base ( B )
an example of - elimination,
(a) Reaction velocity depends only on the concentration of the e.g., CH 3 CH 2 X H 2 C CH 2 ;
Alc.KOH
substrate and the base used; thus reaction is bimolecular reaction. Rate ( HX ) Ethene
[Substrate] [Base]
CH 3 CH CH 3 CH 3 CH CH 2 Alc.KOH
| ( HX )
(b) Since the reaction is a bimolecular reaction, the product Propene
(c) Rearrangement does not take place in E reaction but in case of CH 3 CH 2 CH CH 3 CH 3 CH CH CH 3
Alc.KOH
2
| ( HX ) 2 - Butene (Major)
allylic compound rearrangement is possible. X
(d) Reaction is carried out in the presence of polar aprotic solvent. CH 3 CH 2 CH CH 2
1- Butene (Minor)
(e) The E 2
reaction occurs in one step,
.. (ii) Dehydration of alcohol is another example of elimination
B H H B - - - - H H
| | | reaction. When acids like conc. H 2 SO 4 or H 3 PO4 are used as
CH 3 C C H CH 3 C
Slow step
C H dehydrating agents, the mechanism is E . The proton given by acid is taken
| | | 1
H Br H Br up by alcohol.
TS
Dehydration is removal of H 2 O from alcohols,
CH 3 CH CH 2 BH Br
fast
e.g.,
Conc. H 2 SO 4 , 170 C
(2) Orientation in - elimination reactions : If substrate is CH 3 CH 2 OH H 2 C CH 2
( H 2 O )
unsymmetrical, then this will give more than one product. Major product of
the reaction can be known by two emperical rules. Conc. H 2 SO 4 , 170 C
CH 3 CH 2 CH 2 OH CH 3 CH CH 2
Propan -1 - ol ( H 2 O ) Propene
(i) Saytzeff rule : According to this rule, major product is the most
Dehydration of alcohols is in the order:
substituted alkene i.e., major product is obtained by elimination of H from
Tertiary Secondary Primary
that - carbon which has the least number of hydrogen. Product of the (3) (2) (1)
reaction in this case is known as Saytzeff product.
2° and 3° alcohol by E process and 1° alcohol by E process.
1 2
Cl Alcohols leading to conjugated alkenes are more easily dehydrated than the
2 |
Alc.KOH / alcohols leading to non-conjugated alkenes. CH 2 CH CH CH 3 is
CH 3 CH CH CH 3
CH 3 C CH CH 3 |
| 1 HCl |
OH
CH 3 CH
3 easily dehydrated than
Saytzeff p roduct
CH 3 CH 2 CH CH 3 and so
(ii) Hofmann rule : According to this rule, major product is always |
least substituted alkene i.e., major product is formed from - carbon which OH
has maximum number of hydrogen. Product of the reaction in this case is OH OH OH
known as Hofmann product. > >
CH 3 Br CH 3
| | |
Alc.KOH /
CH 3 C CH 2 CH CH 3 CH 3 C CH 2 CH CH 2
| 2 1 | (iii) Dehalogenation : It is removal of halogens, e.g.,
CH 3 CH 3
Hofmann product CH 2 CH 2 Zn dust H 2 C CH 2 in CH 3 OH , heat
| | (-ZnBr2 ) Ethylene
Br Br
Ethylene bromide
General Organic Chemistry 1027
(iv) Dehydrogenation : It is removal of hydrogen, e.g., (3) Rearrangement or migration to free radical species (Free radical
Cu , 300 C rearrangement) : Those rearrangement reactions in which the migrating
CH 3 CH CH 3
CH 3 C CH 3
| ( H 2 ) || group moves to a free radical centre. Free radical rearrangements are
OH O comparatively rare.
Isopropyl alcohol Acetone
(4) Aromatic rearrangement : Those rearrangement reactions in
Rearrangement reactions which the migrating group moves to aromatic nucleus. Aromatic
The reactions, which involve the migration of an atom or group compounds of the type (I) undergo rearrangements in the manner
mentioned below,
from one site to another within the molecule (nothing is added from
outside and nothing is eliminated) resulting in a new molecular structure, X–Y X–H X–H
are known as rearrangement reactions. The new compound is actually the Y
structural isomer of the original one.
+ +
It is convenient to divide rearrangement reactions into following
types: (I) Y
The element X from which group Y migrates may be nitrogen or
(1) Rearrangement or migration to electron deficient atoms oxygen.
(Nucleophilic rearrangement) : Those rearrangement reactions in which
migrating group is nucleophilic and thus migrates to electron deficient Isomerism
centre which may be carbon, nitrogen and oxygen.
Organic compounds having same molecular formula but differing
Y B B: from each other at least in some physical or chemical properties or both are
|
Y | | | | | known as isomers (Berzelius) and the phenomenon is known as isomerism.
C C C C C C
| | | | The difference in properties of isomers is due to the difference in
X: X X the relative arrangements of various atoms or groups present in their
Bridged or molecules. Isomerism can be classified as follows:
non-classical carbocation
X= Nucleophilic species, Y = Electronegative group, B = Another
nucleophile.
(2) Rearrangement or migration to electron rich atoms (Electrophilic
rearrangement) : Those rearrangement reactions in which migrating group
is electrophile and thus migrates to electron rich centre.
Isomerism
Chain Position Ring chain Functional Meta Tauto - Geometrical Optical Conformational
isomerism isomerism isomerism isomerism merism merism isomerism isomerism isomerism
| | | | Propan -1 - amine
Cl Cl Cl Cl
1, 2 Dichloro propane 1, 3 Dichloro propane H
( , - dihalide)
(Vicdihalide) CH 3 CH 2 N
Aldehydes, carboxylic acids (and their derivatives) and cyanides CH 3
do not show position isomerism. N Methyl ethanamine
n 2n+2
Acetaldoxime Acetamide
C H O : CH 3 CH 2 OH ; H 3 C O CH 3
2 6
Ethyl alcohol Dimethyl ether (4) Ring-chain isomerism : This type of isomerism is due to different
modes of linking of carbon atoms, i.e., the isomers possess either open chain
C H O : CH 3 CH 2 CH 2 OH ; C 2 H 5 O CH 3
3 8 or closed chain sturctures.
n propyl alcohol Ethyl methyl ether
H2
CH O
4 10
: CH 3 CH 2 CH 2 CH 2 OH ; C
n Butyl alcohol
C2 H 5 O C2 H 5 H 2C CH 2
Diethyl ether CH : 6 12
| | ;
(ii) Aldehydes, ketones and unsaturated alcohols …etc. (C H O) H 2C CH 2
n 2n
O C
|| H2
C H O : CH 3 CH 2 CHO ; CH 3 C CH 3 ;
3 6
Cyclohexan e
Propionald ehyde
CH 2 CH 2
Acetone
CH 2 CH CH 3 ; CH 2 CH CH 2 OH | CHCH 3
Allylalcohol C H 2 CH 2 ; CH 3 CH 2CH 2CH 2CH CH 2
O Methyl cyclopentane 1 Hexene
1, 2 Epoxy propane
Ring – chain isomers are always functional isomers.
(iii) Acids, esters and hydroxy carbonyl compounds …etc. (C H O ) n 2n 2
1 Butyne 1, 3 Butadiene organic compounds, then chain or position isomerism is not possible, there
CH 3 C C CH 3 ; H 2C C CH CH 3 will be metamerism e.g.,
2 Butyne 1, 2 Butadiene (a) CH 3 C CH 2 CH 2 CH 3 ;
||
(v) Nitro alkanes and alkyl nitrites ( NO 2 and O N O ) O
(Pentan 2 one)
General Organic Chemistry 1029
(b) CH 3 C CH 2 CH 2 CH 3 ;
|| O OH
| |
O
(Pentan 2 one) CH 3 C CH R CH 3 C CH R
H 2O
OH (Enol)
CH 3 C C H CH 3 are metamers and not chain isomers. (c) Triad system containing nitrogen : Examples
|| | Nitrous acid exists in 2 forms
O CH 3
(3 - Methylbutan - 2 - one) O
H O N O HN
Alkenes does not show metamerism. nitrite form O
Nitro form
(6) Tautomerism
(i) The type of isomerism in which a substance exist in two readily Nitro acinitro system
interconvertible different structures leading to dynamic equilibrium is
known as tautomerism and the different forms are called tautomers (or O O
CH 3 CH 2 N CH 3 CH N
tautomerides). O OH
nitro form (i) Aci form (ii)
The term tautomerism (Greek: tauto = same; meros = parts) was
used by Laar in 1885 to describe the phenomenon of a substance reacting (iii) Characteristics of tautomerism
chemically according to two possible structures. (a) Tautomerism (cationotropy) is caused by the oscillation of
(ii) It is caused by the wandering of hydrogen atom between two hydrogen atom between two polyvalent atoms present in the molecule. The
polyvalent atoms. It is also known as Desmotropism (Desmos = bond and change is accompanied by the necessary rearrangement of single and double
tropos = turn). If the hydrogen atom oscillates between two polyvalent bonds.
atoms linked together, the system is a dyad and if the hydrogen atom (b) It is a reversible intramolecular change.
travels from first to third atom in a chain, the system is a triad. (c) The tautomeric forms remain in dynamic equilibrium. Hence,
their separation is a bit difficult. Although their separation can be done by
(a) Dyad system : Hydrocyanic acid is an example of dyad system in special methods, yet they form a separate series of stable derivatives.
which hydrogen atom oscillates between carbon and nitrogen (d) The two tautomeric forms differ in their stability. The less
atoms. H C N ⇌ C N H stable form is called the labile form. The relative proportion of two forms
varies from compound to compound and also with temperature, solvent etc.
(b) Triad system The change of one form into another is also catalysed by acids and bases.
Keto-enol system : Polyvalent atoms are oxygen and two carbon (e) Tautomers are in dynamic equilibrium with each other and
atoms.
interconvertible (⇌).
Examples : (f) Two tautomers have different functional groups.
O H OH (g) Tautomerism has no effect on bond length.
|| | | (h) Tautomerism has no contribution in stabilising the molecule
C C ⇌ C C and does not lower its energy.
| | (i) Tautomerism may occur in planar or nonplanar molecules.
(Keto) (Enol)
Keto=enol tautomerism is exhibited only by such aldehydes and
Acetoacetic ester (Ethyl acetoacetate) : ketones which contain at least one -hydrogen.
O OH For example
|| |
CH 3 C CH 2 COOC 2 H 5 ⇌ CH 3 C CHCOOC 2 H 5 CH 3 CHO, CH 3 CH 2 CHO, CH 3 COCH 2 COCH 3 etc,.
Keto form (92.1%) Enol form (7.9%)
Tautomerism is not possible in benzaldehyde (C 6 H 5 CHO) ,
Acetoacetic ester gives certain reactions showing the presence of
keto group (Reactions with HCN , H 2 NOH , H 2 NNHC 6 H 5 , etc.) and benzophenone (C 6 H 5 COC 6 H 5 ) , tri methyl acetaldehyde,
certain reactions showing the presence of enolic group (Reactions with (CH 3 )3 C CHO and chloral CCl 3 CHO as they do not have
Na, CH 3 COCl , NH 3 , PCl5 , Br2 water and colour with neutral FeCl3 , H.
etc.). Number of structural isomers
Enolisation is in order
Molecular formula Number of isomers
CH 3 COCH 3 CH 3 COCH 2 COOC 2 H 5 C 6 H 5 COCH 2 COOC 2 H 5
Alkanes
CH 3 COCH 2 COCH 3 CH 3 COCH 2 CHO C4 H10 Two
O Three
||
H
C5 H12
Acid catalysed conversion CH 3 C CH 2 R
Keto C6 H14 Five
OH OH C7 H16 Nine
| |
H
CH 3 C C H R CH 3 C CH R C8 H18 Eighteen
| (Enol form)
H C9 H 20 Thirty five
(Intermediate)
Base catalysed conversion
1030 General Organic Chemistry
C10 H 22 Seventy five The compounds which have same molecular formula but differ in
the relative spatial arrangement of atoms or groups in space are known as
Alkenes and cycloalkanes
geometrical isomers and the phenomenon is known as geometrical
C3 H 6 Two (One alkene + one cycloalkane)
isomerism. The isomer in which same groups or atoms are on the same side
C4 H 8 Six (Four alkene + 2 - cycloalkane) of the double bond is known as cis form and the isomer in which same
groups or atoms are on the opposite side is called trans-isomer.
C5 H10 Nine (Five alkenes + 4 – cycloalkanes)
Examples :
Alkynes
C3 H 4 Two H C COOH H C COOH
|| ||
C4 H 6 Six H C COOH HOOC C H
Maleic acid (cis) Fumaric acid (trans)
Monohalides
C3 H 7 X Two H 3 C C COOH H 3 C C COOH
|| ||
C4 H 9 X Four H C COOH HOOC C H
Citraconic acid (cis- isomer) Mesaconic acid (trans isomer)
C5 H11 X Eight
(1) Conditions for geometrical isomerism : Compound will show
Dihalides geometrical isomerism if it fulfils the following two conditions
C2 H 4 X 2 Two (i) There should be frozen rotation about two adjacent atoms in the
molecule.
C3 H 6 X 2 Four
(a) CC frozen rotation about carbon, carbon double
C4 H 8 X 2 Nine bond in alkenes.
C5 H10 X 2 Twenty one
Alcohols and ethers
Two (One alcohol and one ether) (b) frozen rotation about carbon, carbon single bond in
C2 H 6 O cycloalkanes.
C3 H 8 O Three (Two alcohols and one ether) (c) C N frozen rotation about carbon, nitrogen double
bond in oxime and imine.
C4 H10 O Seven (Four alcohols and three ethers)
(ii) Both substituents on each carbon should be different about
C5 H12 O Fourteen (Eight alcohols and six ethers) which rotation is frozen.
If these two conditions are fulfilled, then compound will show
Aldehydes and ketones geometrical isomerism.
C3 H 6 O Two (One aldehyde and one ketone) The compounds of the following type will not show geometrical
isomerism.
C4 H 8 O Three (Two aldehydes and one ketone)
a C a x C a a C a
C5 H10 O Seven (Four aldehydes and three ketone) || || ||
x C y aC a x C x
Monocarboxylic acids
and esters (2) Distinction between cis- and trans- isomers
Two (One acid and one ester) (i) By cyclization method : Generally, the cis-isomer (e.g. maleic
C 2 H 4 O2 acid) cyclises on heating to form the corresponding anhydride while the
C3 H 6 O2 Three (One acid and two esters) trans-isomer does not form its anhydride.
C4 H 8 O2 Six (Two acids and four esters) H C COOH H C CO
||
Heat
|| O
C5 H10 O2 Thirteen (Four acids and nine esters)
H C COOH H C CO
Maleicacid(cis) Maleic anhydride
Aliphatic amines
C2 H7 N Two (One 1°-amine and one 2°-amine) Note that the two reacting groups (–COOH) are near to each
other.
C3 H 9 N Four (Two 1°-amines, one 2°-amine and one
3°-amine) H C COOH Heat
Eight (Four 1°-amines, three 2°-amines and || No anhydride
C4 H11 N
one 3°-amines) HOOC C H
Fumaric acid (trans)
Aromatic compounds
Four Note that the two reacting groups (–COOH) are quite apart
C8 H 10 from each other, hence cyclisation is not possible.
C9 H 12 Nine (ii) By hydroxylation (Oxidation by means of KMnO4 ,OsO4 or
C7 H 8 O Five H 2 O2 in presence of OsO4 ) : Oxidation (Hydroxylation) of alkenes by
means of these reagents proceeds in the cis-manner. Thus the two
geometrical isomers of an alkene leads to different products by these
Geometrical or cis-trans isomerism reagents. For example,
General Organic Chemistry 1031
H C COOH OH
H COOH
||
KMnO 4
H COOH
H C COOH OH
Maleicacid(cis) meso Tartaricacid
OH
H C COOH H COOH
||
KMnO 4
HOOC C H HOOC H
Fumaric acid (trans )
OH
() Tartaric acid
OH
HOOC H
H COOH
OH
() Tartaric acid