Mechanism of Organic Reactions For UG Students
Mechanism of Organic Reactions For UG Students
Mechanism of Organic Reactions For UG Students
ORGANIC
REACTIONS
B. R. THORAT
GOVT OF MAHARASHTRA
ISMAIL YUSUF
ARTS, SCIENCE
AND
COMMERCE
COLLEGE, MUMBAI
Mechanism of organic reactions
2. Some of the intermediates are stable while some are unstable i.e.
mechanism is theoretical concept.
+
X + X
+ sp2 hybridisation
planar trigonal geometry
having six valance electrons
Different types of carbocations
a. Alkyl carbocations: Alkyl carbocations are stabilized by inductive effect of
substituted alkyl groups.
H + H H + CH3 H + CH3 H3C + CH3
H H CH3 CH3
methyl < primary carbonium < secondary carbonium < tertiary carbonium
+ +
+ +
+
Carbocations (carbonium)
There are various reactions which are generated carbonium ion are-
1. SN1 Reactions:
It is first order nucleophilic substitution reaction having following rate law: Rate
α [Substrate]
e.g. Consider hydrolysis of tert. Butyl bromide. This reaction has been proceeds
in two steps. (a) Ionization of substrate & (b) Nucleophilic attack on
carbonium ion. In the first step of reaction, substrate undergoes ionization
forming carbonium ion. It is planar, sp2 hybridized. Therefore, the solvent
molecule or free electron rich molecule or ion shows nucleophilic attack on
both side of plane and forming racemic product.
Step: I Step: II
CH3 CH3 H3C
H3C CH3
slow + + fast
Br H3C OH + HO
H3C CH3
H3C H3C CH3 H3C CH3 H3C CH3
Planar, SP2 hydridized
OH2
E E X E E X
alkene alkyne
Carbocations (carbonium)
Electrophilic Addition reaction (mechanism):
The mechanism of this reaction has been divided in following steps:
1. Generation of electrophile: It is fast step.
fast E+
E X + X
2. Attack of electrophile: It is slow step; involve the attack of electrophile on
π bond of unsaturated bond orE ring.
+
+
slow
E
alkene
E X E X
The stability order of the carbonium ion is tertiary > secondary > primary >
methyl i.e. thisH reaction
CH3 proceeds
H Hvia more stable
H carbonium.
CH3 H H
+ + Br
+ Br + H C Br
H H3C H
H H H H fast H H 3
H H
major minor
Br 1,2-elimination
H3C H3C + BrH
Carbocations (carbonium)
Electrophilic Elimination reaction: (E1 Mechanism)
It is two step first order mechanism of elimination reaction. The first step
(ionization step) is slow forming carbonium ion while second step of
reaction is fast in which base abstract the proton forming elimination
product.
e.g. Dehydrobromination of 1-bromopropane
HO
Step-I Step II H3C H
CH3 H H3C H H3C H
slow + + fast
H3C H H H + OH2
Br H H3C H H3C H H3C H
Carbonium ion
b. 1,2- shift / migration of adjecent group (stabilisation of carbonium ion): For the
stabilization of carbonium ion, alkyl group shows 1,2-migration along with bonding
pair; result the formation of more stable tertiary carbonium ion.
H3C H3C
+ 1,2-methyl shift +
H3C CH2
H3C H3C CH3
primary carbonium ion tertiary carbonium ion
d. Nature of base and stability of carbonium ion decides the final product.
Carbanions
Organic compound (ion) in which carbon carries negative charge is
called carbanion.
A carbanion is formed by removal of one atom or group of atoms
(which are singly bonded) without bonding pair of electrons i.e.
heterolytic cleavage of bond such that atom or group leaves without
bonding pair. H CH -CHO
Base
CH -CHO
2 2
Nomenclature:-
Named parent alkyl group and adding word carbanion.
CH3-CH2- (CH3)2CH-.
(Ethyl carbanion) (Isopropyl carbanion).
Due to presence of electron pair, they act as Lewis bases or strong
nucleophiles. The acidity of carbon is increased by attaching it to
group which stabilizes the negative charge on it after deprotonation of
proton.
Carbanions
Preparation of carbanions:-
1) Heterocyclic fission of co-valent bond in such a way that a carbon atom
carries a bonding pair of electrons and carries negative charge.
Base Base
H CH2-CHO CH2-CHO CH3-CO-CH2-H CH3-CO-CH2
H-CH2-NO2 CH2-NO2
*
R1 R3 R1 R3
R2 R2
(Carbanion) Umbrella effect
It is assumed that, a carbanion which is stabilized by resonance effect
is SP2 hybridized having planar geometry.
R2
R1
R3 O
Planar hybrid structure
Carbanions
There are several methods for the preparation of carbanion as-
1. Alkylation of carbon acids:
a. Terminal alkynes: Alkynes shows acidic character. In presence of strong bases,
alkyne forming carbanion which can be reacted with alkyl halide forming higher
alkyne. The alkyne carbon is sp hybridized so it stabilizes negative charge.
Base R'-X
R/H H R/H M R/H R'
acetylene metal alkylide higher alkyne
terminal alkyne
Main advantage of this method is, it is used to convert lower alkyne to higher alkyne
without change in functional group.
b. Reactive methylene compounds:
The acidic character of methylene group (-CH2-) can be increased by attaching it to
more electron withdrawing groups such as –CN, -COOR, -CO-, -NO2, etc. After
donation of proton by methylene group forming carbanion, the negative charge
on carbon can be stabilized by –R (resonance) effect.
O O O O O
H R Base R R R R'-X R' R
H H H
R R R R H R
H
O O O O O
Active methylene group
Carbanions
Stability of carbanion of active methylene group:
The hydrogen atom of methylene carbon in EAA is more acidic due to-
1. The electron withdrawing (-I) effect of oxygen atoms, and
2. The resonance stabilisation (-R) of carbanion.
The negative charge on the carbon atom of methylene can be stabilized
by –I and –R effect of the electron withdrawing groups such as –
CN, -COOR, -CO-, -CHO, etc.
O O O O
O O O O
EtONa
H3C OEt H3C OEt
H3C OEt H3C OEt
H
EtOH Carbanion
Carbanions
Applications of ethyl acetoacetate (having reactive methylene group):
a. Synthesis of Succinic acids:
Sodium salt of ethyl acetoacetate reacts with ethyl chloroacetate
followed by hydrolysis gives succinic acid.
O
O O O O O O
EtONa ClCH2 COOEt 1. NaOH OH
H3C OEt H3C OEt H3C OEt 2. H2O/H+ OH
H Carbanion 3.
EtOH CH2CO2Et
O
Succinic acid
b. Synthesis of 4-methyl uracil:
Ethyl acetoacetate (enol form) can be reacts with urea in presence of
phosphoryl chloride to give 4-methyl uracil.
O O
H
NH2 EtO N
POCl3
O + O H
NH2 HO N
H
CH3
Urea EAA CH3
4-methy uracil
Carbanions
c. Synthesis of keto acids:
Sodium diethyl malonate reacts with alkyl halides followed by
hydrolysis and decarboxylation gives 3-keto acid.
COOEt COOEt COOEt +
H3O
COOH
EtONa R-COCl
H H R-CO R-CO
EtOH
H COOEt COOEt COOEt COOH
Diethyl malonate Carbanion -CO2
R-CO-CH2COOH
3-Keto acid
d. Synthesis of α,β-unsaturated acids:
Diethyl malonate reacts with carbonyl compound in presence of base
followed by hydrolysis and decarboxylation gives α,β-unsaturated
acid. COOEt EtONa COOEt
R-COR'
R COOEt HO
+ R COOH
3
H H
EtOH EtONa
H COOEt COOEt R' COOEt R' COOH
Diethyl malonate Carbanion -CO2
R H
R' COOH
Unsaturated acid
Carbanions
e. Synthesis of α-amino acid:
Amino acid (e.g. alanine) can be synthesized by using diethyl malonate
by using following sequence of reactions.
O- H OH O OH
O
H
H
H CH3
H CH3
alkoxide of aldol 3-hydroxybutanal (aldol)
Carbon radicals
The C-C or C-X bond undergoes homolytical cleavage forming intermediate in
which both bonding atoms carries one electron called as free radical. These
intermediates are neutral.
C C
. 2 C
Free radicals are obtained by using reagent such as halogens, AIBN, Me3SiI, etc
photochemically or thermally.
e.g. Chlorination of alkane such as methane.
Cl2 Cl2 Cl2
CH4 + Cl2 CH3Cl CH2Cl2 CHCl3 CCl4
Cl
. + Cl
. Cl2
.
CH3 + CH3
. CH3-CH3
Carbon radicals
Reaction of free radicals:
a. Addition to C=C bond:
Free radicals such as chlorine adds to C=C bond forming another
new free radical. It is further reacts chlorine radical or C=C bond
forming new alkyl radical and so on.
Cl2 Cl
. + Cl
.
. .CH .
Cl
H2C CH2 + Cl 2
CH2-Cl Cl-CH2 CH2-Cl
.CH
CH2-Cl
2
Cl-CH2-CH2-CH2-CH2-Cl
RO OR 2 RO
. .
RO + HBr ROH + Br
.
2. Propagation: The bromine radical reacts with alkene forming more stable allky
radical.
R-CH=CH2 + Br . .
R-CH-CH Br +
.
2 R-CHBr-CH 2
sec. radical (stable) prim. radical (less stable)
Carbon radicals
3. Termination:
The newly formed alky radical (tertiary > secondary > primary) reacts further with
HBr and get terminated and forming bromine radical. Continue this process further.
.
R-CH-CH Br .
2 + HBr RCH2CH2Br + Br
sec. radical (stable)
e. Polymerisation:
Free radical are very reactive (short lived) and reacts with the unsaturated system
forming new radical which is again reacts with alkene and so on forming higher
wieght radical. It is get terminated at the end of reaction.
e.g.: Initiation
RO OR 2 RO
. CH2=CH2 + RO
. .
ROCH2-CH2
Propogation:
. . CH2=CH2
ROCH -CH
2 2 + CH2=CH2 ROCH2CH2CH2CH2 and so on
Termination
. R-H
RO(CH2CH2) CH2CH3
RO(CH2CH2) CH2CH2
n
termination can be done by disproportion, combination, by using trapping agent etc.
Carbon radicals
f. Redox reaction:
Oxidation and reduction with inorganic ions that can change their
valence state by gain or loss of a single electron can be used for the
production of free radical.
e.g. Fe2+ can be used catalyst for the oxidation in presence peroxide.
Ferrous can be convert to ferric (oxidation), so peroxide is convert to
hydroxide anion and free radical (Fenton’s reagent).
Hydroxide radical abstract hydrogen from hydrocarbon forming new
carbon radical. 2+ 3+ - .
Fe + H2O2 Fe + HO + HO
C6H5-CH3 + HO
. .
C6H5-CH2 + OH2
3+ . 2+
C6H5-CHO + Fe C H -CO +
6 5 Fe + H+
Carbon radicals
f. Redox reaction (Kolbe’s Electrolytic method):
Concentrated aqueous solution of sodium salt of carboxylic acids are
electrolyzed forming alkene called as Kolbe’s reaction.
R
O
R
: + CO
Ketene Singlet/triplet
Structure of carbene:
The carbene contain two non-bonding electrons and also two orbitals.
According to the nature of these (non-bonding) electrons, carbene can
be classified into singlet or a triplet state. These electrons are exist
either in one orbital with opposite spins (paired) or in two orbitals of
equal energy with parallel spins.
R1 R1
R1 R2 + R3
R2 R2
Triplet SP 125-1400
Carbonium ion SP2 1200
In the singlet carbene, the electron repulsion energy is higher than the
triplet state carbene. The triplet state carbene is more stable than the
singlet carbene present at ground state (triplet state). This can be
confirmed by electron spin resonance (esr) study. The aryl and diaryl
carbene is present at triplet state in ground state. The triplet carbene is
not linear but bond angle of 125-1400.
Carbene
Reaction of carbene:-
1. Insertion reaction : Carbene undergoes insertion reactions in which
carbenes are inserted into a C-H bond. The reaction may be
intermolecular or intramolecular.
a. Intermolecular:- H
H + : CX 2
CX2
H X X
H + : CX2 . + . CX H
2
H
X X
b. Intramolecular:-
R'' R'
R' H R'' CH2
R + R
R H HC : R' R''
c. Carbene can be reacted with many nucleophiles. e.g.:- Diphenyl
carbene can be inserted into the –OH group of alcohol.
X2C X X
(Trans)
Tautomerism
A phenomenon by which single compound can be exist two or more
easily interconvertable forms, these structures or forms are markedly
differ the relative positions of at least one atom (generally hydrogen) is
called as tautomerism and the structures are called tautomers of each
others.
1. Keto enol system: All aldehydes or ketones containing α-hydrogen
atom are exist in two isomeric forms keto-form and enol-form.
O OH
H
keto form enol form
2. O
- +
O MgI
H2O/H +
OH
H3C Mg I + MgI(OH)
H3C H H3C CH3 H3C CH3
H H
Acetaldehyde Sec (2-propanol) alcohol
alkoxide intermediate
3. HO - O O O
-
O -
H -
O O O-
NaOH
C H H2C H H2C H + H
H2 H3C H H2C H
Carbanion enolate ion H C
Acetaldehyde Acetaldehyde enolate ion alkoxide of ald
OH
O O- H OH O
H
H
H CH3
H CH3
alkoxide of aldol 3-hydroxybutanal (aldol)
Test No 2 (10 Marks)
Answers
4. Cl2 2 Cl
.
. . CH3Cl + Cl
. .
CH2Cl + HCl
CH4 +
.
CH + Cl
Cl CH +
CH3Cl +
3
HCl
Cl
. CH2Cl + Cl2
. CH2Cl2 + Cl
.
3 2
CH2Cl2 + Cl
. .CHCl + HCl CHCl3 + Cl
. .
CCl3 + HCl
.CHCl CHCl3 +
2
. . .
2 + Cl2 Cl CCl3 + Cl2 CCl4 + Cl
5.
e.g. Dehydrobromination of 1-bromopropane
HO
Step-I Step II H3C H
CH3 H H3C H H3C H
slow + + fast
H3C H H H + OH2
Br H H3C H H3C H H3C H
Carbonium ion
Thanks for your good Attention