Hydrocarbons Final PDF

RSM79Ph-IVHCCH1
1. IIT-JEE Syllabus
ALKANE: Physical properties of alkane (melting point, boiling point and density),
combustion and halogenation of alkanes. Preparation of alkane by Wurtz coupling
and decarboxylation reaction.
ALKENE AND ALKYNE: Structure and physical properties of alkenes and alkynes
(boiling point, density, dipole moment), acidity of alkynes. Preparation of alkenes
and alkynes by elimination reaction. Electrophilic addition reaction of alkenes with
Br2, HOCl. Reactions of alkynes: Metal acetylides.
2. Alkanes
Alkanes are open-chain (acyclic) hydrocarbons comprising the homologous series with
the general formula, CnH2n+2, where n is an integer. They have only single bonds and
therefore are said to be saturated.
2.1 Free Rotation about the Carbon-Carbon Single Bond: Conformations
H H Ethane Molecule
H
C 1.53 Å
o
109.5
109.5 o
H C
H H
Electron diffraction and spectroscopic studies have verified this structure in all respects,
giving the following measurements for the molecule : bond angles, 109.5o; C-H length,
1.10Å; C-C length, 1.53 Å. Similar studies have shown that with only slight variations,
these values are quite characteristic of C-H and C-C bonds and of carbon bond angles
in alkanes.
This set of bond angles and bond lengths still does not limit the molecule of ethane to a
single arrangement of atoms, since the relationship between the hydrogens of one
carbon and the hydrogens of the other carbon is not specified. Different arrangement of
atoms that can be converted into one another by rotation about single bonds are called
Conformations. Arrangement I is called the eclipsed conformation and arrangement II
is called its staggered conformation.
H H
H H
H H
H H
H
H H
H Sawhorse Representation
Eclipsed Staggered II
I
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RSM79Ph-IIIHCCH2
H
H H
H H
Newman
Projection
H H
H H
H H
H
Eclipsed I Staggered II
Exercise 1: i) Write down the order of energy of eclipsed and staggered conformation
for ethane molecule.
ii) The number of conformation for a single bond are
a) 1 b) 2
c) 6 d) infinite
The IUPAC system of alkane nomenclature is based on the simple fundamental principle
of considering all compounds to be derivatives of the longest single carbon chain
present in the compound. The chain is then numbered from one end to the other, the
end chosen as number 1 is that which gives the smaller number at the first point of
difference.
CH3 CH3
H3C
H3C CH3 CH3

2-methylpentane 3-methylhexane
When there are two or more identical appendages - the modifying prefixes di-, tri-, tetra-,
penta-, hexa-, and so on are used, but every appendage group still gets its own number.
CH3 CH3 CH3

H3C CH3
CH3 H3C CH3

H3C CH3
2,2-dimethylpentane 2,2,4,4-tetramethylpentane
When two or more appendage locants are employed, the longest chain is numbered
from the end which produces the lowest series of locants. When comparing one series of
locants with another, that series is lower which contains the lower number at the first
point of difference.
CH3 CH3
H3C H3C CH3

H3C CH3 CH3
H3C
CH3 CH3 CH3 CH3 CH3
2,3-dimethylpentane 2,5,6-trimethyloctane 2,2,4-trimethylpentane
(not 3,4,7-trimethyloctane) (not 2,4,4-trimethjylpentane)
Several common groups have special names that must be memorized by the student.
CH3 CH3 CH3

| | |
CH3 CH– CH3CH CH2– CH3–CH2–CH–
isopropyl isobutyl sec-butyl
CH3 CH3
| |
CH3 C– CH3–C–CH2–
| |
CH3 CH3
tert-butyl neo-pentyl
or t-butyl
A more complex appendage group is named as a derivative of the longest carbon chain
in the group starting from the carbon that is attached to the principal chain. The
description of the appendage is distinguished from that of the principal chain by
enclosing it in parentheses.
CH3
|
H–C–CH3
|
H–C–CH3
| 
CH3CH2CH2CH2CHCH2CH2CH2CH3
5-(1,2-dimethylpropyl)nonane
When two or more appendages of different nature are present, they are cited as prefixes
in alphabetical order. Prefixes specifying the number of identical appendages (di, tri,
tetra and so on) and hyphenated prefixes (tert-or t, sec-) are ignored in alphabetizing
except when part of a complex substituent. The prefixes cyclo-, iso-, and neo-count as a
part of the group name for the purposes of alphabetizing.
When chains of equal length compete for selection as the main chain for purposes of
numbering, that chain is selected which has the greatest number of appendage attached
to it.
CH3
CH3
CH3
CH3
H3C
H3C
When two or more appendages are in equivalent positions, the lower number is
assigned to the one that is cited first in the name (that is one that comes first in the
alphabetic listing).
H3C CH3
H3C CH3 CH3
CH3
H3C H3C CH3
3-ethyl-5-methylheptane 4-ethyl-5-isopropyloctane
CH3 CH3
H3C
H3C
CH3
CH3
CH3
CH3 H3C
6-ethyl-3,3-dimethyloctane 6-ethyl-2-methyloctane
3,3,6 is lower than 3,6,6, at first point of difference 2,6 is lower than 3,7
[The complete IUPAC rules actually allow a choice regarding the order in which
appendage groups may be cited. One may cite the appendages alphabetically, as
above, or in order of increasing complexity].
Exercise 2: Write the UPAC name for the following
CH3 CH3
H3C
H3C
i) H3C CH3 ii) H3C
CH3
CH3 CH3
CH3 CH3
H3C CH3
H3C
iii) iv)
CH3
H3C CH3
CH3
CH3
2.2 Preparation of Alkanes
Reactions with No Change in Carbon Skeleton
1. Reduction of Alkyl Halides (RX, X = F, Cl, Br or I)
(Substitution of halogen by hydrogen)

a) RX + Zn: + H+  RH + Zn2+ + X-
b) 4RX + LiAlH4  4RH + LiX + AlX3 (X  F)
or RX + H:(–)  RH + X– (H– comes from LiAlH4)
c) RX + (n - C4H9)3 SnH  R-H + (n - C4H9)3 SnX
d) via organometallic compounds (Grignard Reagent). Alkyl halides react with

either Mg or Li in dry ether to give organometallics having a basic
carbanionic site.
dry ether
RX + 2Li  R Li + LiX then R Li + H2O  RH + LiOH
- + - +
dry ether
X
RX + Mg  R (Mg X) - +
then, RMgX + H2O  RH + Mg
(Grignard Reagent) OH
The net effect is replacement of X by H.
2. Hydrogenation of C=C (alkenes)
CH3 CH3
| Pt. |
CH3-C=CH2 + H2  CH3-CH-CH3
Exercise 3: i)
A 

Na
. Identify A
D.E.
ii) How many hydrocarbon can be obtained by reacting the

H3C Br
H3C
and Br
H3C H3C
with Na in presence of D.E.
Preparation of Alkanes with More C's than the Starting Compounds
Two R groups can be coupled by reacting RBr, RCl or RI with Na or K, yields of

product are best for 1o (60%) and least for 3o (10%) alkyl halides (Wurtz
Reaction).
2RX + 2Na  R-R + 2NaX

2Na + 2CH3CH2CH2Cl  CH3CH2CH2CH2-CH2CH3 + 2NaCl
A superior method for coupling is the Corey House Synthesis.
R MgX or RLi  R-R' (R = 1o, 2o or 3o; R' = 1o)
CuX
RX
3. By heating a mixture of the sodium salt of a carboxylic acid and soda-lime

R CO2Na + NaOH (CaO)  RH + Na2CO3
This process of eliminating CO2 from a carboxylic acid is known as
decarboxylation.
4. Kolbe's electrolytic method : A concentrated solution of the sodium or

potassium salt of a carboxylic acid is electrolysed.
2 RCOOK + 2H2O  R-R + 2CO2 + H2 + 2KOH
Exercise 4: i)
  A
1 eq. Br2
h
ii)
 B 
NBS
 C
LiAlH4
Identify A, B and C
2.3 Homolytic Bond Dissociation Energies and the Relative Stabilities of Radicals
Homolytic bond dissociation energies provide a convenient way to estimate the relative
stabilities of radicals. The energy required to break covalent bonds homolytically is
called homolytic bond dissociation energy and abbreviated by the symbol Ho. We find
the following values of Ho for the primary and secondary C-H bonds of propane.
CH3CH2CH2-H (CH3)2CH-H
(Ho = 98 k cal mol-1) (Ho = 94.5 k cal mol-1)
This that for the reaction in which the designated C-H bonds are broken homolytically,
the values of Ho are those given below:
CH3CH2CH2-H  CH3CH2CH2 + H  Ho = + 98 k cal mol-1

(Propyl radical a 1o radical)
CH2-CH-CH3  CH3  CHCH3 + H Ho = + 94 k cal mol-1

| (Isopropyl radical
H a 2o radical)
These reaction differ in the amount of energy required and in the type of carbon radical
being produced. More energy must be supplied to produce a primary alkyl radical from
propane than is required to produce a secondary carbon radical from the same
compound. This must mean than the primary radical has absorbed more energy and
thus has greater potential energy. As the relative stability of a chemical species is
inversely related to its potential energy, the secondary radical must be more stable than
the primary radical by 3.5 k cal . mol-1.
CH3 CH3
| |
CH3-C-CH2-H  CH3-C-CH3 + H ? Ho = +91 k cal mol-1

|
H tert-Butyl radical (3o)
CH3 CH3
| | 
CH3-C-CH2-H  CH3-CH-CH2 +H ? Ho = +98 k cal mol-1
|
H Isobutyl radical (1o)
The tertiary radical is more stable than the primary radical by 7 k cal mol-1. The kind of
pattern that we find in these examples is found with alkyl radicals generally; overall their
relative stabilities are the following: Tertiary > Secondary > Primary > Methyl
2.4 General Chemical Properties of the Alkanes
Halogenation: Chlorination may be brought about by photo irradiation, heat or catalysts,

and the extent of chlorination depends largely on the amount of chlorine used. A mixture
of all possible isomeric monochlorides is obtained, but the isomers are formed in
unequal amounts, due to difference in reactivity of primary, secondary and tertiary
hydrogen atoms.
The order of ease of substitution is
Tertiary Hydrogen > Secondary Hydrogen > Primary Hydrogen
Chlorination of isobutane at 300 oC gives a mixture of two isomeric monochlorides:
CH3 CH3
| |
CH3-CH-CH2 -Cl and CH3-C- CH3
(67%) (33%) |
Cl
The tertiary hydrogen is replaced about 4.5 times as fast as primary hydrogen.
Bromination is similar to chlorination, but not so vigorous. Iodination is reversible, but it
may be carried out in the presence of an oxidising agent such as HIO3, HNO3 etc., which
destroys the hydrogen iodide as it is formed and so drives the reaction to the right, e.g.
CH4 + I2 CH3I + HI
5HI + HIO3 3I2 + 3H2O
Iodides are more conveniently prepared by treating the chloro or bromo derivative with
sodium iodide in methanol or acetone solution. e.g
RCl + NaI   RI + NaCl

acetone
This reaction is possible because sodium iodide is soluble in methanol or acetone,

whereas sodium chloride and sodium bromide are not. This reaction is known as
Conant Finkelstein reaction.
Direct fluorination is usually explosive; special conditions are necessary for the
preparation of the fluorine derivatives of the alkanes.
RH + X2 

uv
RX + HX
or Δ
(Reactivity of X2: F2 > Cl2 > Br2; I2 does not react)
The mechanism of methane chlorination is:
Initiation Step: Cl : Cl 


uv
2Cl H = + 243 KJ mol-1
or Δ
The required enthalpy comes from ultraviolet (uv) light or heat.
Propagation Step
i) H3C : H + Cl  H3C + H : Cl H = - 4KJ mol-1 (rate determining)
ii) H3C + Cl : Cl  H3C : Cl + Cl H = - 96 KJ mol-1
The sum of the two propagation steps in the overall reaction,
CH4 + Cl2  CH3Cl + HCl H = - 100 KJ mol-1
In propagation steps, the same free radical intermediates, here Cl and H3C, being
formed and consumed. Chains terminate on those rare occasions when two free-radical
intermediates form a covalent bond.
Cl + Cl  Cl2 ; H3C + Cl  CH3 : Cl
H3C + CH3  H3C : CH3
Inhibitors stop chain propagation by reacting with free radical intermediates, e.g.
.. .. .. ..
H3C + . O  O .  H3C O — O. . .
.. .. ..
In more complex alkanes, the abstraction of each different kind of H atom gives a
different isomeric product. Three factors determine the relatives yields of isomeric
product.
Reactivity-Selectivity Principle
1. Probability Factor: This factor is based on the number of each kind of H atom in
the molecule. For example, in CH3CH2CH2CH3 there are six equivalent 1o H’s
and four equivalent 2o H’s. The ratio of abstracting a 1oH are thus 6 to 4,
or 3 to 2.
2. Reactivity of H : The order of reactivity of H is 3o > 2o > 1o.
3. Reactivity of X : The more reactive Cl is less selective and more influenced by
the probability factor. The less reactive Br is more selective and less influenced
by the probability factor, as summarized by the Reactivity-Selectivity Principle.
If the attacking species is more reactive, it will be less selective, and the yields
will be closer to those expected from the probability factor.
CH3 Cl2 / h CH3

   +
H3C 25C H3C Cl H3C
butane (28%) (72%)
CH3
CH3 CH3 H3C

Cl
Cl2 / h
    Cl +
H3C CH3 light, 25 C H3C H3C
CH3
(64%) (36%)
CH3   
Br2 , light

+ CH3
H3C 127 C H3C Br H3C
Br
(2%) (98%)
CH3 H3C
H3C CH3 CH3
 
Br2 , light
Br +
127C H3C
H3C
CH3 Br
trace (over 99%)
In the chlorination of isobutane abstraction of one of the nine primary hydrogens leads to
the formation of isobutyl chlorides, whereas abstraction of a single tertiary hydrogen
leads to the formation of tert-butyl chloride. The probability favour formation of isobutyl
chloride by the ratio of 9:1. But the experimental results show the ratio roughly to be 2:1
or 9:4.5. Evidently, about 4.5 times as many collisions with the tertiary hydrogen are
successful as collisions with the primary hydrogens. The Eact is less for abstraction of a
tertiary hydrogen than for abstraction of a primary hydrogen.
The rate of abstraction of hydrogen atoms is always found to follow the sequence
3o > 2o > 1o. At room temperature, for example, the relative rate per hydrogen atom are
5.0:3.8:1.0. Using these values we can predict quite well the ratio of isomeric
chlorination products from a given alkane. For example:
CH3CH2CH2CH3  CH3CH2CH2CH2Cl + CH3CH2CHClCH3

Cl2
light, 25 C
n  butylchloride no.of1o H reactivityof1o H

 
sec  butylchloride no.of 2 o H reactivityof 2 o H
6 1.0 6 28%
   equivalent to
4 3.8 15.2 72%
Inspite of these differences in reactivity, chlorination rarely yields a great excess of any
single isomer.
The same sequence of reactivity, 3o > 2o > 1o, is found in bromination, but with
enormously larger reactivity ratios. At 127oC, for example, the relative rates per
hydrogen atom are 1600:82:1. Here, differences in reactivity are so marked as vastly to
outweigh probability factors. Hence bromination gives selective product.
In bromination of isobutane at 127oC,
Isobutylbromide no.of 1o H reactivity of 1o H

 
tert  butylbromide no.of 3o H reactivity of 3o H
9 1 9
  
1 1600 1600
Hence, tert-butyl bromide happens to be the exclusive product (over 99%).
3. Alkenes
3.1 Nomenclature and Structure
Alkenes (olefins) contains the structural unit
C=C
and have the general formula CnH2n. These unsaturated hydrocarbons are isomeric with
the saturated cycloalkanes.
CH3CH = CH2 H2C CH2

C3H6 CH2
Propylene Cyclopropane
The C=C consists of a  bond and a  bond, in a plane at right 

angles to the plane of the single  bonds to each C. The 
bond is weaker and more reactive than the  bond. The H H

reactivity of the  bond imparts the property of unsaturation to C—C
alkenes; alkenes therefore readily undergo addition reactions. H H
The  bond prevents free rotation about the C=C and therefore
an alkene having two different substituents on each doubly
bonded C has geometric isomers. For example, there are two Fig. 1
2-butenes :
H3C CH3 H CH3

C=C C=C
H H H3C H
CH3’s on opposite sides :
CH3’s on same side
called trans-
called cis-
Geometric (cis - trans) isomers are stereoisomers because they differ only in the spatial
arrangement of the groups. They are diastereomers and have different physical
properties (m.p., b.p., etc.). In place of cis-trans, the letter Z is used if the higher - priority
substituents on each C are on the same side of the double bond. The letter E is used if
they are on opposite sides.
The IUPAC rules for naming alkenes are similar in many respects to those for naming
alkanes.
1. Determine the base name by selecting the longest chain that contains the double
bond and change the ending of the name of the alkane of identical length from
ane to ene.
2. Number the chain so to include both carbon atoms of the double bond, and
begin numbering at the end of the chain nearer the double bond. Designate the
location of the double bond by using the number of the first atom of the double
bond as prefix :
CH3 CH3
H2C H3C
but-1-ene (2E)-hex-2-ene
3. Indicate the locations of this substituent groups by the numbers of the carbon
atoms to which they are attached.
CH3
CH3
CH3
H3C H3C H2C Cl
CH3
CH3 H3C 4-chlorobut-1-ene
2,5-dimethylhex-2-ene (2E)-5,5-dimethylhex-2-ene
4. Two frequently encountered alkenyl groups are the vinyl group and the allyl
group.
CH2 = CH — CH2 = CH CH2 —

The vinyl group The allyl group
The following examples illustrate how these names are employed
CH2 = CH — Br CH2 = CH — CH2 Cl

vinyl bromide allyl chloride
5. The geometry of the double bond of a disubstituted alkene is designated with the
prefixes, cis and trans. If two identical group are on the same side of the double
bond, it is cis, it they are on opposite sides; it is trans.
Cl Cl Cl H
C=C C=C
H H H Cl
cis - 1,2 - Dichloroethene trans - 1,2 - Dichloroethene
3.2 The (E) - (Z) System for Designating Alkene Diastereomers
The term cis- and trans-, where, when used to designate the stereochemistry of alkene
diastereomers, are unambiguous, only when applied to disubstituted alkenes. If the
alkene is trisubstituted or tetrasubstituted, the terms cis and trans are either ambiguous
or do not apply at all. In the following alkene, it is impossible to decide whether A is cis
or trans since no two groups are the same.
Br Cl
H F
A newer system is based on the priorities of groups in the Cahn - Ingold - Prelog
convention. This system called the (E) - (Z) system, applies to alkene diastereomers of
all types. In the (E) - (Z) system, we examine the two groups attached to one carbon
atom of the double bond and decide which has the higher priority. Then we repeat the
operation at the other carbon atom.
Cl F F Cl Higher priority
Higher priority
Higher priorityBr H Higher priorityBr H

(E)
(Z)
We take the group of higher priority on one carbon atom and compare it with the group
of higher priority on the other carbon atom. If two groups of higher priority are on the
same side of the double bond, the alkene is designated (Z). If the two groups of higher
priority are on opposite sides of the double bond, the alkene is designated (E). The
following examples illustrate this :
H3C CH3 Cl Cl
CH > H
CH > H Br > Cl
H H H Br
(2Z)-but-2-ene (E)-1-bromo-1,2-dichloroethylene
Cl Br
H Cl
(Z)-1-bromo-1,2-dichloroethylene
Example: The IUPAC name for

CH2 H3C CH3
H3C
H3C
CH3
CH2
CH3 H3C CH3 vinylcyclopropane
(4Z)-4-(1-methylbutyl)hexa-1,4-diene (4E)-7-ethyl-4,8-dimethyldec-4-ene
H H H3C H
H3C
CH3 H
H H H2C
(2Z,4Z)-hexa-2,4-diene (3E)-penta-1,3-diene
Exercise 1: i) CH3
H2C
CH3
H3C
H3C CH2
ii)
CH3
H3C CH3
iii)
CH3
3.3 Relative Stabilities of Alkenes
Heats of Hydrogenation: Hydrogenation provides a way to measure the relative

stabilities of certain alkenes. The reaction of an alkene with hydrogen is an exothermic
reaction; the enthalpy change involved is called the heat of hydrogenation. Most alkenes
have heats of hydrogenation near - 30 kcal mol-1.
For example,
Pt
CH3CH2CH =CH2 + H2  CH3CH2CH2CH3 H = -30.3 Kcal mol
-1
1 - Butene
CH3 CH3
C=C + H2 
Pt
CH3CH2CH2CH3 H = -28.6 Kcal mol-1
H H
cis –2 - Butene
H3C H
Pt
 CH3CH2CH2CH3 H = -27.6 Kcal mol
-1
C=C + H2
H CH3
trans –2 - Butene
In each reaction the product is the same. A different amount of heat is evolved in each
and this difference is related to different relative stabilities of the individual butenes.
1-Butene evolves the greatest amount of heat when hydrogenated, and trans-2 butene
evolves the least. Hence, 1-butene must have the greatest potential energy and be the
least stable isomers. Trans - 2 butene must have the lowest P.E and be the most stable
isomer.
3.4 Preparation of Alkenes
Cracking of petroleum hydrocarbons is the source of commercial alkenes.

H H
| |
a) —C—C— Pt or Pd — C = C — + H2 (Mainly a special industrial process)
| | | |
Most alkenes are made in the laboratory by -elimination reactions.
H X
| |
b) B: + — C — C —  — C = C — + B : H + X- (Dehydrohalogenation)
| | | |
KOH in ethanol is most often used as the source of the base, B: , which then is
C2H5O-.
H OH
| |
c) —C—C— acid — C = C — + H2O (Dehydration)
| | | |
Br Br
| |
d) Mg(or Zn) + — C — C —  — C = C — + MgBr2(or Zn Br2) (Dehalogenation)
| | | |
In dehydration and dehydrohalogenation the preferential order for removal of an

H is 3° > 2° > 1° (Saytzeff Rule). We can say “the poor gets poorer.” That is
because the more R’s on the C = C group, the more stable is the alkene. The
stability of alkenes in decreasing order of substitution by R is,
R2C = CR2 > R2C = CRH > R2C = CH2 ; RCH = CHR > RCH = CH2 > CH2 = CH2
e) Alkynes can also be partially reduced to alkenes.
R R
cis-alkene
Lindlar catalyst
H H
R R
R H
Na/Liq. NH3
trans-alkene
H R
Discussion
1. Dehydrohalogenation of Alkyl Haldies : 1, 2 - Elimination
When isopropyl bromide is treated with a hot concentrated alcoholic solution of a strong
base like potassium hydroxide, there is obtained propylene.
+ KOH 2  H3C

C H5OH
H3C CH3 + KBr + H2O
heat
CH2
Br
This is an example of dehydrohalogenation : 1,2-elimination of the elements of

hydrogen halide. Dehydrohalogenation involves elimination- of the halogen atom and
the hydrogen atom from a carbon
X
-
C C C C + HB + X
H
B
adjacent to the one losing the halogen. The reagent required is a base, whose function
is to abstract the hydrogen as a proton.
This is called 1,2-elimination : for the double bond to form, the hydrogen must come
from a carbon that is adjacent to the carbon holding the halogen. Now the carbon
holding the halogen is commonly the -carbon. Any carbon attached to the -carbon is
a -carbon, and its hydrogens are -hydrogens. Elimination, then, involves loss of a -
hydrogen. In some cases, dehydrohalogenation, yields a single alkene and in other
cases a mixture. We can expect an alkene corresponding to the loss of any one of the
-hydrogens but no other alkenes. n-Butyl bromide, for example, can lose hydrogen
only from C-2.
Examples : (Principal product in each reaction is underlined)
a) CH3
Br CH3 H2C
 but-1-ene
H
b) Br
CH3 CH3 + CH3

H3C H2C H3C
cis and trans
c) Br
CH3
H3C CH3
CH3 cis & trans
d) Br CH3
H3C CH3
CH3 +
H3C H2C CH3 H3C CH3
e) H3C
CH3 CH3 CH3
H3C +
Br H3C CH3 H3C CH3
H3C
CH3 CH3
cis & trans CH3
H3C CH3
+
CH2
Dehydrohalogenation belongs to a general class of reaction: 1,2-elimination.
Such elimination reactions are characterized by the following :
a) The substrate contains a leaving group, an atom or group that leaves the molecule,
taking its electron pair with it.
b) In a position  to the leaving group, the substrate contains an atom or group - nearly
always hydrogen- that can be abstracted by a base, leaving its electron pair behind.
c) Reaction is brought about by action of a base.
Typically, the base is a strongly basic anion like hydroxide, or an alkoxide derived from
an alcohol : ethoxide, C2H5O-., tert-butoxide, (CH3)3CO-; etc.
In elimination, a good leaving group is a weakly basic anion or molecule, just as in

nucleophilic substitution. As a weak base, it readily releases a proton; as a good leaving
group, it readily releases carbon. In dehydrohalogenation the leaving group is the very
weakly basic halide ion. Other substrates which can release weakly basic anions are
sulfonates.
Heterolytic bond dissociation energies show that strength of carbon-halogen bonds

follow the sequence,
Heterolytic bond
dissociation energy R-F > R-Cl > R-Br > R-I
In these elimination reactions the reactivity of alkyl halides follows the sequence,
Reactivity toward E2 R-I > R-Br > R-Cl > R-F
The E2 Mechanism
The reaction involves a single step : base pulls a proton away from carbon ;
simultaneously a halide ion departs and the double bond forms. Halogen takes an
electron pair with it ; hydrogen leaves its electron pair behind, to form the double bond.
What characterizes this particular mechanism is that they are all happening
simultaneously, in a single step, via a single transition state:
X
-
C C C C + HB + X
H
B
In this T.S, two bonds are being broken : C-H and C-X. This energy for bond breaking
comes from bond-making : formation of the bond between the proton and the base, and
the formation of  bond. As the base begins to pull the proton away from the molecule,
the -carbon, armed with the electron pair begin to form a bond to the -carbon-the 
bond. As the  bond starts to form, the carbon-halogen bond starts to break : the  bond
making helps to supply energy for the C-halogen bond-breaking.
The rate-determining step, the only step, involves reaction between a molecule of alkyl
halide and a molecule of base, and its rate is proportional to the concentration of both
reactants. This mechanism was named E2, that is elimination, bimolecular.
Rate = K[RX][:B] E2 reaction

Second-order kinetics.
The best stereospecific conformation for E2 elimination is an anti-coplanar conformation

with H and L 180 apart which permits the approaching electron-rich base to be at a
maximum distance from the electron-rich leaving group.
B
H
R
R
R
R
X
If we consider the dehydrohalogenation of the alkyl halide 1-bromo -1,2-

diphenylpropane. This compound exists as two pairs of enantiomers.
C6H5 C6H5 C6H5 C6H5
H3C H H H H3C H H3C H
Br H H Br H Br H H
C6H5 C6H5 C6H5 C6H5

(I) (II) (III) (IV)
The product, too, exists as stereoisomers : a pair of geometric isomers Z and E.
With I and II, we obtain only the Z isomer.
C6H5 H CH3
H3C
H3C H
H3C C6H5 H C6H5
Br H
C6H5
C6H5 Br H5C6
[(Z)-1-methyl-2-phenylvinyl]benzene
If we start with III and IV, we obtain only the E alkene.
C6H5 H CH3
H3C
H3C H
H3C C6H5 H C6H5
H Br
H
C6H5 Br H5C6
[(Z)-1-methyl-2-phenylvinyl]benzene
An Exception to Saytzeff’s Rule
Carrying out dehydrohalogenations with a base such as potassium tert-butoxide in tert-

butyl alcohol favours the formation of the less substituted alkene:
H3C H3C CH3 CH2

CH3 CH3 
+  
75 C
+
( CH3 )3 COH
H3C - H3C
O Br H3C CH3 H3C CH3
When an elimination yields the less substituted alkene, we say that it follows the
Hofmann rule.
2. Dehydration of Alcohols
Heating most alcohols with a strong acid causes them to lose a molecule of water (to
dehydrate) and form an alkene.

C C 

H
C C + H2O
heat
OH
The reaction is an elimination and is favoured at higher temperatures. The most

commonly used acids in the laboratory are Bronsted acids - proton donors such as
sulphuric acid and phosphoric acid. Lewis acids such as alumina (Al2O3) are often used
in industrial, gas phase dehydrations.
Dehydration reactions of alcohols show several important characteristics which shall be

explained.
i) The experimental conditions-temperature and acid concentration-that are

required to bring about dehydration are closely related to the structure of
the individual alcohol. Alcohols in which the hydroxyl group is attached to a
primary carbon (primary alcohols) are the most difficult to dehydrate.
Dehydration of ethanol, for example, requires concentrated sulphuric acid and a
temperature of 180C.
H3C    H2C
conc. H2SO4

CH2 + H2O
180 C
OH
Secondary alcohols usually dehydrate under milder conditions. Cyclohexanol,

for example, dehydrates in 85% phosphoric acid at 165-170C.
OH
 
85% H3PO4
+ H2O
165 170 C
Tertiary alcohols are usually so easily dehydrated that extremely mild conditions
can be used, ter-butyl alcohol, for example, dehydrates in 25% H2SO4 at a
temperature of 85C.
H3C H3C CH2

CH3
 
20% H2SO4
+ H2O
85 C
H3C
OH CH3
Thus, overall, the relative ease with which alcohols undergo dehydration is in the
following order
Ease of Dehydration
R R H
R OH R OH R OH
R H H
3° alcohol 2° alcohol 1° alcohol
This behaviour, is related to the stability of the carbocation formed in each

reaction.
ii) Some primary and secondary alcohols also undergo rearrangements of their
carbon skeleton during dehydration.
Exercise 2: i) Write down the possible number of geometrical isomer of

2,4-hexadiene
ii) Arrange the following alkenes in there increasing order of stability.
CH3 CH3
a) H C b) H C
2 3
H3C CH3 H H
c) c)
H3C CH3 H H
Mechanism of Alcohol Dehydration: An E1 Reaction
The mechanism is an E1 reaction in which the substrate is a protonated alcohol (or an

alkyloxonium ion). We consider the dehydration of CH3CHOHCH3 that proceeds through
a carbonium ion intermediate. A catalytic role is assigned to the acid and O in ROH is a
basic site.
Step 1: H3C CH3

+ H3C CH3
H
HO +
O H2
Step 2: H3C CH3

H3C CH3
+
O +
H H
Step 3: H3C CH3 H3C CH2
Instead of HSO4-, a molecule of alcohol could act as a base in step 3 to give ROH2+.
Because step 2 is then, the rate determining step, it is the step that determines the
reactivity of alcohols toward dehydration. The formation of a tertiary carbocation is

easiest because the free energy of activation for step 2 of a reaction leading to a tertiary
carbocation is lowest. The order of reactivity of the alcohols reflects the order of stability
of the incipient carbonium ion (3>2>1).
Enthalpy ?+
R CH2 --- OH2
?? ??
R2 CH --- OH2
??
?? ??
R3 C --- OH2
:
?H ?H
:
?H
:
+
RCH2 R2CH2
+
+
R3C
Primary Secondar Tertiary
y
+
RCH2 OH2 R2CH OH2
+ +
RC OH2
Reaction Progress
Carbocation Stability and the Occurrence of Molecular Rearrangements
Let us consider the rearrangement that occurs when 3,3-dimethyl-2-butanol is

dehydrated.
CH3 CH3 CH3
H3C
CH3  85% H3PO4
+ CH3
heat CH3
H3C H3C H2C
OH CH3
CH3
(major) (minor)
The first step of this dehydration is the formation of the protonated alcohol in the usual
way. In the second step the protonated alcohol loses water and a secondary
carbocation is formed. Next the less stable, secondary carbocation rearranges to a
more stable tertiary carbocation.
CH3
H3C CH3
+ H3C + C CH3
CH  +
CH3 H3C
CH3  ~C H3
H3C
H3C + CH3
CH3
CH3 3° carbocation
T.S. (more stable)
The rearrangement occurs through the migration of an alkyl group (methyl) from the
carbon adjacent to the one with positive charge. The methyl group migrates with its
electron pair, i.e., as a methyl anion, -:CH3. After the migration is complete, the carbon
atom that the methyl anion left has become a carbocation and the positive charge on the
carbon atom to which it migrated becomes neutralized. Because a group migrates from
one carbon to the next, this kind of rearrangement is often called a 1,2-shift. The final
step of the reaction, is the loss of proton from the new carbocation, and the formation of
an alkene.
H3C
(a)
H2C
Less stable alkene
CH3
H
CH3
CH3
+
H C H3C
CH3
CH3 (b) H3C
CH3 More stable alkene
CH3
Path (b) leads to the highly stable tetrasubstituted alkene, and this path is followed by
most of the carbocations. Path (a) leads to the less stable, disubstituted alkene and
produces the minor product of the reaction.
The formation of the more stable alkene is the general rule (Saytzeff’s rule) in the
acid-catalyzed dehydration of alcohols.
Reactions involving carbocations show that rearrangements are general phenomena.

They occur almost invariably when the migration of an alkanide ion or hydride ion can
lead to a more stable carbocation. The following are examples.
CH3 CH3
+
H3C CH 2   
methanide
C CH3
migration +
H3C
CH3 (3°)
H CH3
+
H3C CH   
hydride
C CH3
migration +
H3C
CH3 CH3
(3°)
Rearrangements of carbocations can also lead to the change in ring size, as the
following example shows:
CH3
CH3 
CH
OH  
H , heat +
( H2O ) CH3
CH3
2° carbocation
CH3
CH3 + CH3 CH3
+ H

CH3
CH3
H
Exercise 3: Arrange the following in increasing order of dehydration
OH OH OH
OH
(I) (II) (III) (IV)
3. Alkenes by Debromination of Vicinal Dibromides
Vicinal (or vic) dihalides are dihalo compounds in which the halogens are situated on
adjacent carbon atoms. The name geminal (or gem) dihalide is used for those dihalides
where both halogen atoms are attached to the same carbon atom. Vic-dibromides
undergo debromination when they are treated with a solution of sodium iodide in
acetone or a mixture of Zn dust in acetic acid (or ethanol).
+ 2NaI 
acetone
C C C C + I2 + 2NaBr
C C   
CH3CO 2H
C C + ZnBr2
or CH3CH2OH
Debromination by sodium iodide takes place by an E2 mechanism similar to that for

dehydrohalogenation.
Br
- -
I + C C C C + IBr + Br
Br
- -
I + IBr I2 + Br
4. Conversion to Alkanes
RCH = CHR + H2   RCH2CH2R (Heterogeneous catalysis). The relative

Pt, Pd or Ni
rates of hydrogenation
H2C=CH2 > RCH=CH2 > R2C=CH2, RCH=CHR > R2C=CHR > R2C=CR2
Indicate that the rate is decreased by steric hindrance.

H
R R
+ H2     
[BH3 ] CH3COOH R
R from B 2H6 R R
BH2 Homogeneous
Alkyborane
 
RCH  CHR
NH 2NH 2  
H2 O 2
2
 [NH  NH]  RCH 2CH 2R  N  N
Hydrazine Cu Dimide
3.5 Electrophilic Polar Addition Reactions
Table shows the results of electrophilic addition of polar reagents to ethylene.

Reagent Product
Name Structure Name Structure
Halogens (Cl2, Br2 only) X:X Ethylene dihalide CH2XCH2X
Hydrohalic acids H:X Ethyl halide CH3CH2X
Hypohalous acids X:OH Ethylene halohydrin CH2XCH2OH
Sulfuric acid (cold) H:OSO2OH Ethyl bisulfate CH3CH2OSO3H
Water (dil. H3O+) H:OH Ethyl alcohol CH3CH2OH

Borane (CH3CH2BH2)
H2B:H Ethyl borane
(CH3CH2)3B
Peroxyformic acid H:O  OCH = O

Ethylene glycol CH2OHCH2OH
(HCO3H)
i) Addition of Hydrogen Halides to Alkenes
Markovnikov’s Rule: Hydrogen halides (HCl, HBr and HI) add to the double bond of
alkenes :
C C + HX C C
H X
Mechanisms for addition of hydrogen halide to an alkene involves the following two
steps :
Step 1: H
-
C C + H-X  
slow
C C + X
+
Step 2: H H
-
C
+
C + X 
fast
C C
H X H
The addition of HBr to some alkenes give a mixture of the expected alkyl bromide and
an isomer formed by rearrangement.
CH3
H3C Br CH3
+ 2-methylpentane
CH3 
H3C CH


H CH3
H2C
H
CH3 CH3 CH3 CH3
+ 
H3C C 
Br
H3C
CH3 Br
H3C
2-bromo-2-methylbutane
With this understanding of the mechanism for the ionic addition of hydrogen halides to
alkenes, a statement can be made :
In the ionic addition of an unsymmetrical reagent to a double bond, the positive portion
of the reagent attaches itself to a carbon atom of the double bond so as to yield the more
stable carbocation as intermediate. Because this is the step that occurs first, it is the
step that determines the overall orientation of the reaction.
When HI is added to 1-butene the reaction leads to the formation 2-iodobutane, that
contains a stereocenter.
CH2 CH3
+ HI H3C
H3C
The product, therefore, can exist as a pair of enantiomers. The carbocation that is
formed in this first step of the addition is trigonal planar and is achiral. When the iodide
ion reacts with this flat carbocation, reaction is equally likely at either face. The reaction
leading to the two enantiomers occur at the same rate, and the enantiomers, therefore,
are produced in equal amounts as a racemic form.
Exercise 4: i) Give the mechanism for the following conversion

CH 2OH
ii) CH3
H3C C CH  A, identify A.

HCl
CH3 CH2
ii) Addition of Water to Alkenes: Acid Catalyzed Hydration
The acid-catalyzed addition of water to the double bond of an alkene is a method of

preparation of low molecular weight alcohols. The addition of water to the double bond
follows Markovnikov’s rule.
CH3
H3C
OH
H
+ HOH 

H3C CH2 
25 C H3C
CH3
As the reactions follow M.R, acid-catalyzed hydration of alkenes do not yield primary
alcohols except in the special case of the hydration of ethene. The occurance of
carbocation rearrangements limits the utility of alkene hydrations as a laboratory method
for preparing alcohols. Oxymercuration-demercuration, allows addition of H and OH
without rearrangements. Another called hydroboration-oxidation, permits the anti-
Markovnikov and syn-addition of H and OH.
iii) Oxymercuration-Demercuration
Alkenes react with mercuric acetate in the presence of water to give hydroxymercurial
compounds which on reduction yield alcohols.
Oxymercuration Demercuration
C C + H2O + Hg(OAc)2 C C  

NaBH4
C C
OH HgOAc OH H
The first stage, oxymercuration, involves addition of -OH and HgOAc to the C-C double
bond. Then, in demercuration, HgOAc is replaced by H. The reaction sequence
amounts to hydration of the alkene, but is much more widely applicable than direct
hydration.
Oxymercuration-demercuration gives alcohols corresponding to Markovnikov addition of

water to the carbon-carbon double bond. For example :
H3C CH3
CH2   
Hg( OAc )2 , H2O
 H3C
NaBH4
OH
CH3
CH3
 

Hg( OAc )2 , H2O NaBH4
OH
CH3 CH3
H3C H3C
CH2 CH3
  
Hg( OAc )2 , H2O

NaBH4
H3C H3C
OH
iv) Hydroboration-Oxidation
With the reagent diborane, (BH3)2, alkenes undergo hydroboration to yield alkylboranes,
R3B, which on oxidation gives alcohols. For example :
Hydroboration Oxidation
C C + H-B C C   
H2O 2 / O H
C C
H B H OH
Alcohol
The hydroboration oxidation process gives products corresponding to anti-Markovnikov

addition of water to the C-C double bond. This reaction is free from rearrangement.
Examples
CH3 CH3

  
(BH3 )2
 
H2O2 .OH
OH
H3C CH2 H3C
OH
CH3 
OH
H3C   
(BH3 )2
  H3C
H2O 2 .OH
CH3 CH3
CH3 CH3

H3C   
(BH3 )2
 
H2O 2 .OH
H3C OH
CH3 CH2 CH3
Exercise 5: i) An Olefines was treated with ozone and the resulting product on
reduction (reductive ozonolysis) gave 2-pentanone and
acetaldehyde. What is the structure of olefin? Write the reaction
ii) How many gm of Br2 will reaction with 5 gm of (a) Pent-1-ene; (b)
Pent-1-yne; (c) Pentanes.
v) Addition of Bromine And Chlorine To Alkenes
Alkenes react rapidly with bromine at room temperature and in absence of light. If
bromine is added to an alkene, the red-brown colour of the bromine disappears almost
instantly as long as the alkene is present in excess. The reaction is one of addition .
+ Br2  
CCl 4 rapid decolourization of Br2/CCl4
C C C C
r .t.
is a test for alkenes and alkynes
Br Br
Vic-Dibromide
R R
R R R
R R R

 OH
R R + MnO2
O O H2O
severtal steps
R R Mn OH R
-
O O
Cl
CH3 + Cl 2  
 9 C
CH3
H3C H3C
Cl
Br
H
5C
+ Br2   + eantiomer
CCl 4 Br
H
(1R,2R)-1,2-dibromocyclohexane
Mechanism of Halogen Addition
The mechanism proposed for halogen addition is an ionic mechanism.
In the first step the exposed electrons of the  bond of the alkene attack the halogen in
the following way:
  C
C -
+
Br Br Br + Br
C
C
Bromonium ion Bromide ion
As the  electrons of the alkene approach the bromine molecules, the electrons of the
bromine-bromine bond drift in the direction of the bromine atom more distant from the
approaching alkene. The bromine molecule becomes polarised as a result. The more
distant bromine develops a partial negative charge ; the nearer bromine becomes
partially positive. Polarization weakens the bromine-bromine bond, causing it to break
heterolytically. A bromide ion departs, and a bromonium ion forms. In the bromonium
ion a positively charged bromine atom is bonded to two carbon atoms by two pairs of
electrons : one pair from the  bond of the alkenes, the other pair from the bromine
atom.
In the second step, one of the bromide ions produced in step 1 attacks one of the carbon
atoms of the bromonium ion. The nucleophilic attack results in the formation of a vic-
dibromide by opening the three-membered ring.
C Br C
+
- Br
Br
C
Br
When cyclopentene reacts with bromine in CCl4, anti-addition occurs and the products of
the reaction are trans-1,2-dibromocyclopentane enantiomers (as a racemate).
Br H


Br2
+ enantiomer
CCl4
H Br
When cis-2-butene adds bromine, the product is a racemic form of 2-3-dibromobutane.

When trans-2-butene adds bromine the product is the meso compound. Thus we find
that a particular stereoisomeric form of the starting material react in such a way
that it gives a specific stereoisomeric form of the product. Thus the reaction is
stereospecific.
Br CH3
H H Br
H H CH3
H CH3 Br H
CH3 Br
CH3
H3C
H CH3
(2Z)-but-2-ene
Br CH3 Br H
Br H Br
H CH3
CH3
Br CH3
H H Br
H H3C CH3
H3C H H Br
CH3 Br
CH3
H
(2E)-but-2-ene H CH3
Br CH3 H Br
Br H Br
H3C H
CH3
Halohydrin Formation
If the halogenation of an alkene is carried out in aqueous solution (rather than in CCl4),
the major product of the overall reaction is a halo-alcohol called a halohydrin. In this
case, the molecules of the solvent becomes reactants, too.
C C + X2 + H2O C C + C C + HX
X OH X X
X = Cl2 or Br2
Halohydrin formation can be explained by the following mechanism :
R R R R
-
+ X-X R R + X
+
R R X
+
R R R OH2 R OH
+
R R + H2 O R R -H
R R
+
X -
X R X R
If the alkene is unsymmetrical, the halogen ends up on the carbon atom with greater
number of hydrogen atoms.
H3C OH
CH2   H3C

Br2 , H2O
or HOBr
H3C CH3 Br
vi) Radical Addition to Alkenes : The Anti-Markovnikov Addition Of Hydrogen

Bromide
Alkenes in the presence of organic peroxides reacts with hydrogen bromide, undergoes
anti-Markovnikov addition. Hydrogen flouride, hydrogen chloride, and hydrogen iodide
do not give anti-Markovnikov addition even when peroxides are present.
The mechanism for anti-Markovnikov addition of HBr is a radical chain reaction initiated
by peroxides:
Initiation Steps
R  O  O  R  2RO ( O  O  bond is weak)

RO + HBr  Br + ROH
Propagation steps for chain reaction
CH3CHBr  CH2 X CH3CH = CH2 + Br  CH3CH  CH2Br (2 radical)
(1 radical)
CH3 CHCH2Br + HBr  CH3CH2CH2Br + Br
The Br generated in the second step continues the chain.
vii) Syn-Hydroxylation
Hydroxylation with permanganate is carried out by reaction at room temperature of the

alkene and aqueous permanganate solution ; either neutral or slightly alkaline.
Hydroxylation is a very good method for the synthesis of 1,2-diols.
HO
H2C CH2 + aq. KMnO4
OH
ethylene glycol
H3C
OH
H3C  
1. OsO 4
2. NaHSO3 / H2O
CH2 OH
propylene glycol
The mechanism for the formation of glycols by permanganate ion and osmium tetroxide
involves the formation of cyclic intermediates. Then in several steps cleavage at the
oxygen-metal bond takes place ultimately producing the glycol and MnO2 or Os metal.
The course of these reactions is syn-hydroxylation.
R R R R R R

R R OH
 R R + MnO2
H2 O
several steps
R R O O OH OH
Mn
-
O O
+ MnO2 
cold

H H
H2O / OH
OH OH
cis-1,2-cyclopentanediol
Cis-2-butene when treated with cold alkaline aqueous KMnO4 gives meso glycol and
trans-2-butene gives the racemate.
viii) Oxidative Cleavage of Alkenes
Alkenes are oxidatively cleaved by hot alkaline permanganate solution. The terminal CH2
group of 1-alkene is completely oxidized to CO2 and water. A disubstituted atom of a
double bond becomes  C  O group of a ketone.
A monosubstituted atom of a double bond become aldehyde group which is further

oxidised to salts of carboxylic acids.
Examples:
O
 
CH3
  2CH3
KMnO 4 , OH


H
2CH3CO 2H
H3C heat
-
(2E)-but-2-ene O
Acetate ion
CH2  O
H3C
  H3C
KMnO 4 , OH
+ H2O
H
CH3 CH3
CH3 O
CH3
CH3 
 
KMnO 4 , OH
+
H3C H HO CH3
H3C O
CH3 O OH

 
KMnO 4 , OH
H H3C O
CH3 OH H3C O

 
KMnO 4 , OH +
H3C CH3 H
H3C O
H3C OH
Ozonolysis of Alkenes
A more widely used method for locating the double bond of an alkene involves the use of
ozone (O3). Ozone reacts vigorously with alkenes to form unstable compounds called
initial ozonides, which rearranges spontaneously to form compounds known as
ozonides. Ozonides, themselves are unstable and reduced directly with Zn and water.
The reduction produces carbonyl compounds that can be isolated and identified.
R R
R R R
R O R
R


O3
  2
H2O / Zn
O + Zn(OH) 2
R
O O O O
R
O
CH3
CH3
CH2  
i ) O3
+ HCHO
ii) H2O / Zn
H3C
H3C CH3
CH3
CH3
CH3  
i ) O3
+ CH 3CHO
ii) H2O / Zn
H3C
H3C CHO
H O
O
CH3   i ) O3
H3C ii) H O / Zn
2
H3C H
CH3
CH3 CH3
  2CH 3COCH 3 + OHC - CH 2COCH 3

i ) O3
H3C CH3 ii) H2O / Zn
H CH3
CH3 O O
  2HCHO
i ) O3
+
H2C CH2 ii) H2O / Zn
H3C H
ix) Substitution Reactions at Allylic Position
Cl 2 + H2C  H2C

high
+ HCl
temperature Cl
CH3
Br2 + H2C  H2C

low
+ HBr
conc. of Br2 Br
CH3
The low concentration of Br2 comes from N-bromosuccinamide (NBS)
N Br (N.B.S.)
O
SO2Cl2 + H2C = CHCH3 
 H2C = CHCH2Cl + HCl + SO2
UV or
peroxides
These halogenations are like free radical substitution of alkenes. The order of reactivity
of H-abstraction is allyl>3>2>1>vinyl.
4. Alkynes
4.1 Electronic Structure of the Triple Bond
Acetylene is known experimentally to have a linear structure. The C  C distance of 1.20

Å is the shortest carbon-carbon bond length known. The carbon-hydrogen bond length of
1.06 Å is shorter than that in ethylene (1.08 Å) or in ethane (1.10 Å) (Figure 1). These
structural details are readily interpreted by an extension of the - electronic structure of
double bonds. In acetylene the -framework consists of Csp-hybrid orbitals as indicated
in figure 2.
The sp2-s -bonds are shorter than are sp3-s -bonds. The trend also holds for the sp-s
bonds in acetylene. The effect of the amount of s-character in the carbon-hydrogen bond
distance is shown graphically in figure 3. Superimposed on the -electrons are two
orthogonal -electron systems as shown in figure 4.
1.061 Å 1.203Å
H —— C  C – H
180°
Figure : 1 Structure of acetylene.
HIS-Csp Csp-Csp Csp -HIS
H C C H
Figure : 2 -electronic
framework of acetylene.
1.11
1.10 3
sp (ethane)
1.09
1.08 2
sp (ethylene)
1.07
1.06 sp (acetylene)
1.05
20 30 40 50
s-character in carbon orbital, %
Figure : 3 Relationship between carbon-hydrogen bond distance and the approximate amount of s-
character in carbon orbital.
Figure : 4 -system of acetylene.
The symbolic representations in figure 4 are actually misleading because the electrons
in two orthogonal p-orbitals form a cylindrically symmetrical torus or doughnut-like
electron density distribution.
4.2 Nomenclature of Alkynes
The simple alkynes are readily named in the common system as derivatives of acetylene
itself.
CH3C  CH CH3—CC—CH2—CH3 F3CCCH

methylacetylene ethylmethylacetylene trifluoromethylacetylene
In the IUPAC system the compounds are named as alkynes in which the final – ane of
the parent alkane is replaced by the suffix – yne. The position of the triple bond is
indicated by a number when necessary.
CH3C  CH (CH3)2CHCCH CH3CH2CH2CHC  CCH3

Propyne 3-methyl –1-butyne
CH2CH2CH3
4-propyl-2-heptyne
If both –yne and –ol endings are used, the –ol is last and determines the numbering
sequence.
HC  CCH2CH2OH HOCH2CCCH2OH
3-butyn-1 ol 2-butyn –1,4-diol
When both a double and triple bond are present, the hydrocarbon is named an alkenyne
with numbers as low as possible given to the multiple bonds. In case of a choice, the
double bond gets the lower number.
CH3CH = CHC  CH HCCCH2CH=CH2

3-penten-1-yne 1-penten –4-yne
(not 2-penten-4-yne) (not 4-penten –1-yne)
In complex structures the alkynyl group is used as a modifying prefix.
C CH
ethynylcyclopentane
4.3 Physical Properties
The physical properties of alkynes are similar to those of the corresponding alkenes. The
lower members are gases with boiling points somewhat higher than those of the
corresponding alkenes. Terminal alkynes have lower boiling points than isomeric internal
alkynes and can be separated by careful fractional distillation.
The CH3-C bond in propyne is formed by overlap of a Csp3 -hybrid orbital from the methyl
carbon with a Csp-hydrid from the acetylenic carbon. The bond is C sp 3 -Csp. Since one
orbital has more s-character than the other and is therby more electronegative, the
electron density in the resulting bond is not symmetrical. The unsymmetrical electron
distribution results in a dipole moment larger than that observed for an alkene, but still
relatively small.
CH3CH2CCH CH3CH2CH=CH2 CH3CCCH3

 = 0.80 D  = 0.30 D =0D
Symmetrically disubstituted acetylenes, of course, have no net dipole moment.
4.4 Acidity of Alkynes
The hydrogens in terminal alkynes are relatively acidic. Acetylene itself has a pKa of
about 25. It is a far weaker acid that water (pKa 15.7) or the alcohols (pKa 16-19), but it is
much more acidic than ammonia (pKa 34). A solution of sodium amide in liquid ammonia
readily converts acetylene and other terminal alkynes into the corresponding carbanions.
RCCH + NH2–  RC  C— + NH3
This reaction does not occur with alkenes or alkanes. Ethylene has a pKa of about 44
and methane has a pKa of about 50.
From the foregoing pK'as we see that there is a vast difference in the stability of the
carbanions RC  C—, CH2 = CH—, and CH3—. This difference may readily be explained in
terms of the character of the orbital occupied by the lone-pair electrons in the three
anions. Methyl anion has a pyramidal structure with the lone-pair electrons in an orbital
1 3 
that is approximately sp3  s and p  . In vinyl anion the lone-pair electrons are in an
4 4 
1 2  1 1 
sp2-  s and p  orbital . In acetylide ion the lone pair is in an sp-orbital  s and p  .
3 3  2 2 
sp3
sp2
sp
H H -
-
C C=C -
H H H H-CC
H
methyl anion vinyl anion acetylide ion
Electrons in s-orbitals are held, on the average, closer to the nucleus than they are in p-
orbitals. This increased electrostatic attraction means that s-electrons have lower energy
and greater stability than p-electrons. In general, the greater the amount of s-character
in a hybrid orbital containing a pair of electrons, the less basic is that pair of electrons,
and the more acidic is the corresponding conjugate acid.
CH3: CH4
base CH2 = CH: CH2 = CH2 acid
strength HC  C: HCCH strength
Of course, the foregoing argument applies to hydrogen cyanide as well. In this case, the
conjugate base, NC—, is further stabilized by the presence of the electronegative
nitrogen. Consequently, HCN is sufficiently acidic (pKa 9.2) that it is converted to its salt
with hydroxide ion in water.
HCN + OH— CN— + H2O
Alkynes are also quantitatively deprotonated by alkyllithium compounds, which may be

viewed as the conjugate bases of alkanes
CH3(CH2)3CCH + n-C4H9Li  CH3(CH2)3CCLi + n-C4H10
The foregoing transformation is simply an acid-base reaction, with l-hexyne being the
acid and n-butyllithium being the base. Since the alkyne is a much stronger acid than the
alkane (by over 20 pK units), equilibrium lies essentially completely to the right.
Terminal alkynes give insoluble salts with a number of heavy metal cations such as Ag+
and Cu+. The alkyne can be regenerated from the salt, and the overall process serves as
a method for purifying terminal alkynes. However, many of these salts are explosively
sensitive when dry and should always be kept moist.
CH3(CH2)3CCH + AgNO3  CH3(CH2)3CCAg + HNO3
4.5 Preparation Of Alkynes
Acetylene
Acetylene itself is formed from the reaction of the inorganic compound calcium carbide
with water.
CaC2 + 2 H2O  Ca(OH)2 + HC  CH
This method was once an important industrial process for the manufacture of acetylene.
However, the method has now been replaced by a process in which methane is
pyrolyzed in a flow system with short contact time.
1500°C HC  CH + 3 H2
2CH4
0.01 – 0.1 sec.
This reaction is endothermic at ordinary temperatures, but is thermodynamically favored

at high temperatures.
Laboratory Methods of Preparation
1. Dehydrohalogenation of vic-Dihalides or gem-Dihalides
H X H H H
—C—C— or —C—C— Alc. KOH KX + H2O + — C = C —
H X X X X
A gem-dihalide A vic - dihalide
A vinyl halide
NaNH2
NaX + NH3 + —C C—
The vinyl halide requires the stronger base sodamide (NaNH2).
2. Dehalogenation of vic-Tetrahalogen Compounds
CH3—CBr2—CBr2— CH3 + 2Zn EtOH

heat CH3—CC—CH3 + 2ZnBr2
2,2,3,3-Tetrabromobutane 2-butyne
This reaction has the drawback that the halogen compound is itself prepared by
halogen addition to alkynes.
3. Alkyl Substitution in Acetylene; Acidity of  C-H

NaNH2  NH3

RCCH +  or  RCC : Na+ +  or
 Na 1 H
 2 2
R—C  C–: + 1°R — CH2 X  R—CC–CH2—R + X– (SN2 mechanism)
There is a fair amount of variety possible using this method. Acetylene itself may
be alkylated either once to make a terminal alkyne or twice to make an internal
alkyne.
liq. NH3
HCCH + NaNH2 HCCNa
+ n-C4H9Br CH3(CH2)3CCH
–33°C
1-hexyne
2NaNH2 2 n–C3H7Br
HCCH CH3CH2CH2CCCH2CH2CH3
liq.NH3
–33°C 4-octyne
Since acetylide ions are highly basic, competing elimination is a common side
reaction. The products of such an elimination reaction are an alkene (from the
alkyl halide) and an alkyne.
Br
– –
RC C : + H——CH2 —— CHR  CH2 = CHR + Br + RC C–H
In practice, the alkylation of acetylene or another terminal alkyne is only a good

method for the syntheiss of alkynes when applied to primary halides that do not
have branches close to the reaction centre. With secondary halides, and even
with primary halides that have branches close to the reaction center, elimination
is usually the major reaction.
Illustration 1: Outline a synthesis of propyne from isopropyl or propyl bromide. The

needed vic-dihalide is formed from propene, which is prepared from the
alkyl halides.
Solution:
CH3 CH 2 CH 2 Br 
n  Pr opyl bromide 
 alc . alc . NaNH
or  CH3  CH  CH 2  CH3 CHBrCH2 Br
Br2
CH3 CHCHBr 
2  CH C  CH
3
CH3 CHBrCH3  KOH KOH
Isopropyl bromide 
Illustration 2: Synthesize the following compounds from HCCH and any other organic
and inorganic reagents (do not repeat steps):
(a) 1-pentyne, (b) 2-hexyne.
Solution: a) HCCH
 
  H  C  C : N a 3 
 H  C  C  CH 2CH 2CH 3
NaNH 2 CH CH 2 CH 2I
  CH I NaNH  
b) N a : C  C  H 3  CH  C  C  H 
  
2  CH  C  C : N a
3 3
CH CH CH I
3 
 2 
2  CH  C  C  CH CH CH
3 2 2 3
Exercise 1: a) Br
H3C
  A. Identify A
NaNH2
(Excess)
H3C
CH3 Br
b) CH3 CH3
H3C C HC   B, Identify B

NaNH2
( Excess)
Br Br
4.5 Chemical Properties of Acetylenes
Addition Reactions at the Triple Bond
Nucleophilic  electrons of alkynes add electrophiles in reactions similar to additions to

alkenes. Alkynes can add two moles of reagent but are less reactive (except to H2) than
alkenes.
1. Hydrogen
CH3-C C-CH2CH3 + 2H2 


Pt
CH3CH2CH2CH2CH3
H3C CH3 H3C H

 H2


Na, liq. NH3
Lindlar's catalyst H3C CH3 trans ( anti) addition
cis ( sy)
H H H C2H5
2. HX (HCl, HBr, HI)
CH3-CC-H  CH3-CBr=CH2 

HBr
 CH3-CBr2-CH3
HBr
(Markovnikov addition)
CH3-CC-H + HBr   CH3-CH=CHBr (anti-Markovnikov)

peroxide
3. Halogen (Br2, Cl2)

X X X X
R—CC—H X2 R—C = C — H X2 R—C—C—H
X X
4. H2O (Hydration to Carbonyl Compounds)
When passed into dilute sulphuric acid at 60oC in the presence of mercuric
sulphate as catalyst, acetylene adds on one molecule of water to form
acetaldehyde. The mechanism of this hydration takes place via the formation of
vinyl alcohol as an intermediate.
H2SO4
CH  CH + H2O 2+ [CH2 = CHOH]  CH3CHO
Hg
The homologues of acetylene form ketone when hydrated, example, propyne

gives acetone.
OH O
H2SO4
CH3-CC-H+H2O HgSO4 CH3-C=C-H CH3-C-CH3 (Markovnikov addition)
H
a vinyl alcohol Acetone (unstable)
H
O CH3
+ H2O  
H2SO4
HgSO4
1-phenylethanone
5. Boron Hydride
H2O2,NaOH
R H oxidation
RCH2CHO
R— C  C— H + R2BH  C = C
H BR2 CH3COOH
hydrolysis
RCH= CH2
with dialkylacetylenes, the products of hydrolysis and oxidation are cis-alkenes

and ketones, respectively.
O
CH3 CH3 CH3 CH3
CH3COOH H2O2
C=C C=C B CH3—CH2—C—CH3
0°C NaOH
H H H
H 3
2-Butanone
Cis-2-Butene a vinylborane
6. Dimerization
+ –
Cu(NH3)2 Cl
2 H—C  C — H H2O H2C=CH—CCH
Vinylacetylene
7. Oxidation to Carboxylic Acids
3 CH3CCH + 8KMnO4 + KOH  3CH3COOK + 3K2CO3 + 8MnO2 + 2H2O
CH3CH2CC-CH3 + 2KMnO4  CH3CH2COOK + CH3COOK + 2MnO2 + 2H2O
CH3 CH3
oxdn.
CH3-CH-CC CH2 CH2CH3 CH3CH-CO2H + CH3CH2CH2CO2H
(Two isomeric acids each having M.F. C4H8O2)
8. Ozonolysis-Hydrolysis
1. O3
CH3CCCH2CH3 CH3COOH + HOOCCH2CH3
2. hydrolysis
2-Pentyne Acetic acid Propanoic acid
Acetylene and its homologues form ozonides with ozone, and these compounds
are decomposed by water to form diketones, which are then oxidised to acids by
the hydrogen peroxide formed in the reaction.
O
H2O 1 2 1 2
1 2
R CCR + O3  R C CR
2
R C—CR + H2O2  R CO2H + R CO2H
O O O
O
Acetylene is exceptional in that it gives glyoxal as well as formic acid.

(i) O3
CH  CH OCHCHO + HCO2H
(ii) H2O
9. Nucleophiles
When acetylene is passed into dilute hydrochloric acid at 65oC in the presence
of mercuric ions as catalyst, vinyl chloride is formed :
2
CHCH + HCl 
Hg
 CH2 = CHCl
Acetylene adds on hydrogen cyanide in the presence of cuprous chloride in

hydrochloric acid as catalyst to form vinyl cyanide :
CHCH + HCN  CH2=CHCN
Vinyl cyanide is used in the manufacture of Buna-N-synthetic rubber, which is a

copolymer of vinyl cyanide and butadiene.
10. When acetylene is passed into warm acetic acid in the presence of mercuric ions
as catalyst, vinyl acetate and ethylidene diacetate are formed:
2
CHCH + CH3CO2H 
Hg
 CH2=CHOOCCH3
2
CH2=CHOOCCH3 + CH3CO2H 
Hg
 CH3CH(OOCCH3)2
Vinyl acetate (liquid) is used in the plastics industry. Ethylidene diacetate (liquid),
when heated rapidly to 300-4000C, gives acetic anhydride and acetaldehyde.
11. Acetylene reacts with nitric acid in the presence of mercuric ions to form
nitroform, CH(NO3)3, and combines with arsenic trichloride to form Lewisite.
12. When acetylene is passed into methanol at 160-200oC in the presence of small
amount (1-2 per cent) of potassium methoxide and under pressure just high
enough to prevent boiling, methyl vinyl ether is formed. The mechanism is
believed to involve nucleophilic attack in the first step.
CHCH + CH3O-  CH=CHOCH3 3

 CH2=CHOCH3 + CH3O-
CH OH
Methyl vinyl ether is used for making the polyvinyl ether plastics.
13. Acetylene and formaldehyde interact in the presence of sodium alkoxide as

catalyst to form butynediol, together with smaller amounts of propargyl alcohol :
HCCH + CH3O– HCC— + CH3OH

– — CH3OH
O = CH2 C  CH  O — CH2—C  CH
–
HO — CH2 — C  CH CH3O HOCH2C CCH2OH
CH2O
This reaction in which acetylene (or any compound containing the  CH group,
i.e., a methine hydrogen atom) adds on to certain unsaturated links (such as in
the carbonyl group), is known as ethinylation. Thus the above reactions with
formaldehyde are examples of ethinylation.
14. When acetylene is passed into hypochlorous acid solution, dichloroacetaldehyde

is formed:
CHCH + HOCl  [CHCl=CHOH]   [Cl2CHCH(OH)2] Cl2CHCHO + H2O

HOCl
Dichloroacetic acid, Cl2CHCO2H, is also formed by the oxidation of

dichloroacetaldehyde by the hypochlorous acid.
15. When passed through a heated tube acetylene polymerises, to a small extent, to
benzene.
3C2H2
Homologues of acetylene behave in a similar manner, e.g., propyne polymerises

to 1,3,5-trimethylbenzene, and but-2-yne to hexamethylbenzene:
CH3 CH3
H3C CH3
3H3C 3 H3C
CH H3C CH3 CH H3C CH3

CH3
Under suitable conditions acetylene polymerises to cyclooctatetraene:
4C2H2
16. Reactions as Acids: – CC-H + base  -CC:-
17. Formation of heavy metal acetylides
-CC-H + M+  -CC-M + H+
Examples: H-CC-H + 2Ag+  Ag-CC-Ag + 2H+
Identification of terminal alkynes
Silver acetylide (white ppt.)

CH3-CC-H + Cu (NH3)2+  CH3-CC-Cu + NH4+ + NH3
Cuprous methylacetylide (Red ppt.)
18. Formation of alkali metal acetylides
Example:
H-CC-H + Na   H-CC:- Na+ + 1/2 H2

liq.NH3
Sodium acetylide
CH3—CH—C C— H + NaNH2 ether CH3 — CH — C C : Na + NH3

– +
CH3 CH3
Sodium isoproylacetylide
Illustration 3: Dehydrohalogenation of 3-bromohexane gives a mixture of cis-2-hexene

and trans-2- hexene. How can this mixture be converted to pure
a) cis-2-hexene?
b) trans-2-hexene?
Solution: Relatively pure alkene geometric isomers are prepared by stereoselective

reduction of alkynes.
a) Hydrogenation of 2-hexyne with Lindlar's catalyst gives cis-2-hexene.

CH3CH = CHCH2CH2CH3 Br2 CH3CH—CHCH2CH2CH3 2NaNH2
Br Br
H3C CH2CH2CH3
CH3CCCH2CH2CH3 H2 C=C
Lindlar’s catalyst
H H
cis –2- Hexene
b) Reduction with Na in liquid NH3 gives the trans product.
H3C H
CH3CCCH2CH2CH3 Na C=C
NH3 CH2CH2CH3
H
trans –2- Hexene
5. Solutions to Exercise
ALKANES
Solution 1: i) Energy order – staggered  eclipsed
ii) d) inifinite
Solution 2: i) 3,4,5-trimethyl heptane

ii) 2-ethyl-4-(1-methyl ethyl)octane
iii) 3,4,5,6-tetramethyl octane
v) 4,4-dipropyl heptane
Solution 3:: i) X ii) Three

X
Br
Br
Solution 4: i) ii) iii) C=

A= B=
ALKENES
Solution 1:: i) 3,3-dimethyl-1-butene
ii) 3-(1,2-dimethyl propyl)-1,3-hexadiene
iii) 4-cyclopentyl-2-butene
Solution 2: i) H H H H
H3C H
CH3 CH3
H H H3C H
(I)
(IV)
H3C H H H
H H
H H3C
H CH3 H CH3
(III) (IV)
ii) Stability order
eabcd
Solution 3:: I  II  III  IV
Solution 4: i) +
CH 2OH CH 2OH2



H
-H2O
+
CH3
+

H
 
Ring
Expansion
ii) CH3 CH3

 +
H3C C CH 

H
H3C C CH CH3
CH3 CH2 CH3

2° carbocation
-Metheyl
shift
CH3
CH3 CH3

C CH3
H3C C HC 
 H3C
Cl + CH
Cl CH3 CH3
Solution 5: i)
Alkene is H3C CH 2-CH 2-CH 3
C
HC
CH3
(Z)-3-methylhex-2-ene
H3C-H 2C-H 2C
H3C-H 2C-H 2C O
CH3
CH 
 O3 C
C H3C CH
H3C CH3
O O
H2O/Zn
H3C-H 2C-H 2C CH3
C O + O HC
H3C
ii) H3C CH2 Br

a) CH2 CH
+ Br2 CH2HC
H3C CH2 CH2
pent-1-ene CH 2
Br
70 gm 160 gm
so 5 gm 11.42 gm
H3C CH2 Br Br
b) CH2 C
+ 2Br2 CH 2 C HC
H3C CH2 CH
pent-1-yne Br Br
68 gm 320 gm
so 5 gm 23.53 gm
H3C CH2 CH3

c) CH3CH2CH2CH2CH3 + 1/2Br2
CH2HC
pentane
Br
72 gm 80 gm
so 5 gm 5.55 gm
ALKYNES
Solution 1: a) CH3
H3C C C CH
CH3
(A)
b) H3C
C C CH2
H3C
(B)
6. Solved problems
6.1 Subjective
Problem 1: Starting with benzene, outline a synthesis of

1 - Bromo-2-(trichloromethyl)benzene,,1-Bromo-3-(trichloromethyl)benzene
and 1-Bromo-4-(trichloromethyl)benzene
CH3 CH3 CH3

Solution:

CH3Cl


Br2
+
AlCl3 Fe
Br Br
Cl2 / h Cl2 / h
CCl 3 CCl 3
Br Br
1-bromo-2-(trichloromethyl)benzene 1-bromo-4-(trichloromethyl)benzene
CH3 CCl 3 CCl 3

CH3Cl


Cl2

 Br2
AlCl3 h Fe
Br
1-bromo-3-(trichloromethyl)benzene
Problem 2: Acid catalysed dehydration of neopentyl alcohol (CH 3)3CCH2OH yields 2

methyl 2 butene as the major product. Outline a mechanism showing all
steps in its formation.
Solution: CH3 CH3

+ H3C
H3C  +
 H3C

H CH 2
CH3
CH3 OH CH3
H3C
H3C H
H3C CH3
2-methylbut-2-ene
Problem 3: a) An unknown alkene with the formula C7H12 undergoes oxidation by hot
basic KMnO4 to yield after acidification only one product
C7H12    H3C

i ) hot alk. KMnO 4 COOH

ii) H3 O Identify the alkene.
O
b) Starting with compounds C2H2 & C2H5Br outline a synthesis of meso
3, 4 dibromohexane.
c) How would you distinguish between but-1-yne and but-2-yne.
Solution a) CH3
H3C COOH
  

i ) hot alk. KMnO 4

ii) H3O
O
H CH3
b)
CH     
2 moles of NaNH
  
Na in liq. NH3
2
HC
2 moles of C 2H5Br
H3C CH3
H3C H
Br2 ( anti addition )
C2H5
H Br
H Br
C2H5
c) By passing ammoniacal AgNO3 solution, white ppt. of Ag2C2 is formed

in case of but-1-yne but no white ppt. is formed in case of but-2-yne.
Problem 4: a) How many total stereoisomers are possible for 2, 3 dihydroxy butane.
Out of these how many are optically active and how many are optically
inactive?
b) HO
CH3 H

 A. Identify A with a proper mechanism
CH3
Solution: a) H H
H3C – C* – C* – CH3
(* chiral centre)
OH OH
2, 3 dihydroxy butane
2 chiral centres are present. But it has plane of symmetry. So total no.
of streoisomers are = 3. These are given below.
CH3 CH3 CH3
H OH H OH HO H
H OH HO H H OH
CH3 CH3 CH3
I II III
I is Meso compound II & III exists as enantiomers
 Two (II & III) are optically active and (I) is optically inactive
b) OH
+ + CH3
H
CH3 
 CH3  
Ring exp ansion
CH3 CH3
CH3
CH3
CH3
Problem 5: Identify the products in the following reactions.

a) CH3

NO 2
 
t
Bu
b) H / HBr 
CH3—CH—CH2—CH2—CH3   
OH
c) O
H 

d) Cl
aq.KOH


SN1
e) O O
|| ||
PhMgCl
HO  CH 2  C CH 2  C H 

Solution: a) CH3 b) CH3—CH—CH2CH2CH3
t NO2 Br
Bu
c) O d)
OH
e) PhH
Problem 6: Suggest a mechanism for the dehydration of CH 3CHOHCH3 that proceeds

through a carbonium ion intermediate. Assign a catalytic role to the acid
and keep in mind that the O in ROH is a basic site like O in H 2O.
Solution: CH3––CH––CH3 + H+ Fast CH3––CH––CH3
OH +OH2
Fast +
CH3––CH––CH3 CH3––CH––CH3 + H2O
+OH2

CH3–– C H––CH2+ HSO4
– fast CH3––CH = CH2 + H2SO4
H
H2SO4 act as an acid in first step and base in third step. Since it is
regenerated back it is acting as a catalyst.
Problem 7: List the possible products, in order of decreasing yield, from the reaction
of 3-bromo –2,3 – dimethyl pentane with alcoholic KOH.
Solution: CH3 CH3

alc. KOH 
CH3––CH2––C–––CH––CH3
–HBr
Br
CH3 CH3
CH3––CH2––C = C––CH3 (A)
Tetra alkyl substituted
CH3 CH3
CH3––CH = C––CH––CH3 (B)
trialkyl substituted
CH2
CH3
CH3––CH2––C––CH (C)
CH3
Dialkyl substituted
yield A > B > C

According to saytzeff rule, more substituted alkene is more stable
Problem 8: Account for the formation of both 3 – bromo –2,2– dimethyl butane and
2–bromo –2,3 dimethyl butane from the reaction of HBr with 2,3–dimethyl –
1- butene.
Solution: CH3 CH3

Markonikov addition
CH3––C––CH = CH2 + HBr H3C — C — CH — CH3
CH3 CH3 Br
3 – bromo –2,2 – dimethyl butane.
The reaction steps are

CH3 CH3
+
CH3C — C — C = CH2 + H  H3C — C — CH — CH3 methanide
migration
CH3 CH3
CH3 CH3 CH3

CH3 + –
C–– CH –– CH3 + Br H3C –– C –– CH –– CH3
H3C
Br
2- bromo –2,3 - dimethylbutane
The addition of HBr to some alkene gives a mixture of expected alkyl

bromide and an isomer formed by rearrangement.
Problem 9: One mole of a hydrocarbon (A) reacts with one mole of bromine giving a
dibromo compound C5H10Br2. Substance (A) on treatment with cold, dilute
alkaline KMnO4 solution forms a compound C5H12O2. On ozonolysis (A)
gives equimolar quantities of propanone and ethanal. Deduce the structural
formula of (A).
A   Propanone + ethanal

i) O
Solution: 3
ii) H2
So A
H3C
H3C CH3
2-methylbut-2-ene
H3C Br CH3
+ Br2 H3C
H3C CH3 Br
CH3
2-methylbut-2-ene
2,3-dibromo-2-methylbutane
H3C OH OH
+ alk. KMnO4 H3C
H3C CH3 CH3 CH3
2-methylbutane-2,3-diol
Problem 10: An unsaturated hydrocarbon A (C6H10) readily gives B on treatment with

NaNH2 in liquid NH3. When B is allowed to react with 1-chloropropane a
compound C is obtained. On partial hydrocarbon in the presence of Lindlar
catalyst, compound C gives D (C9H18). On ozonolysis D gives 2, 2-dimethyl
propanal and 1-butanal. With proper reasoning give the structures of A, B,
C and D.
Solution: CH3 CH3

H3C
- +
A= B= H3C C Na
H3C
CH3
H
CH3 CH3
H3C
C= H3C D=
CH3
CH3 CH3 H3C
Problem 11: When gas (A) is passed through dry KOH at low temperature, a deep red
coloured compound, (B) and a gas (C) are obtained. The gas (A), on
reaction with but –2- ene, followed by treatment with Zn/H2O yields
acetaldehyde. Identify (A), (B) and (C)
Solution: (A) O3, (B) KO3, (C) O2
Problem 12: 1,4 – Pentadiene reacts with excess of HCl in the presence or benzoyl
peroxide to give compound (X) which upon reaction with excess of Mg in
dry ether forms (Y). Compound (Y) on treatment ethyl acetate followed by
dilute acid yields (Z). Identify the structures compound (X), (Y) and (Z).
HO
Solution: CH3
H3C
H3C CH3
Cl Cl
H3C
(X) (Z)
MgCl MgCl
H3C CH3
(Y)
Problem 13: There are six different alkane A, B, C, D, E and F. Each on addition of one
mole of hydrogen gives G which is the lowest molecular wt. Hydrocarbon
containing only one asymmetric carbon atom. None of the above alkene
give acetone as a product on ozonolysis. Give the structures of A to F.
Identity the alkenes that is likely to give a ketone containing more than five
carbon atoms on treatment with a warm con solution of alkaline KMnO 4.
Show various configurations of G in fisher projection.
Solution: The 6 different alkenes (A) to (F) are

CH3
CH3
A= B=
CH3
CH3
H3C
H2C
CH3
CH2
C= D=
CH3
CH3 H3C
H3C
CH3 CH3
E= F=
CH3 CH2
H3C H3C
H3C
G= H
H3C
CH3
Problem 14: Two isomeric alkyl bromides A and B (C5H11Br) yield the following results
in the laboratory. A on treatment with alcoholic KOH gives C and D (C 5H10)
C on ozonolysis gives formaldehyde and 2 methyl propanal. B on treatment
with alcoholic KOH gives only C (C 5H10). Deduce the structurers of A, B, C
and D. Ignore the possibility of geometrical and optical isomerism.
Solution: H3C CH3
A= CH3 B= Br
H3C H2C CH3
CH3 CH3
H3C
C= D=
H2C CH3 CH3
Problem 15: With the aid of wedge sawhorse and Newman projections illustrate the
sterechemistry of the products from the E2 – dehydrobrominations of meso
(R,S) –2,3- dibromobutane.
Solution: CH3 CH3 CH3

CH3 CH3
Br
Br H
Br H Br
Br H H Br H
H
CH3
H & Br are anti coplanar
–HBr anti
elimination
CH3
Br CH3
CH3
C
Br
C H
H CH3
6.2 Objective
Problem 1: Anti-Markownikoff addition of HBr is not observed is

(A) Propene (B) 1-Butene
(C) But-2-ene (D) Pent-2-ene
Solution: Both carbons of double bond have equal number of hydrogens and thus it
is symmetrical, alkane.
 (C)
Problem 2: Which of the following reactions will yield 2, 2-dibromopropane?

(A) HC  CH + 2HBr  (B) CH3 – C  CH + 2HB r 
(C) CH3 – CH = CH2 + HBr  (D) CH3 – CH = CH – Br + HBr 
Solution: Br Br
  CH3 – C = CH2 
HBr
CH3 – C  CH Markowniko 
HBr
CH3 – C – CH3
ff addition Markowniko ff addition
Br
 (B)
Problem 3: The products formed by the ozonolysis hydrolysis of compound of formula

C5H8 are CH3 – CH2 – CH2 – COOH and CO2. The compound is
(A) pent-1-yne (B) pent-2-yen
(C) pent-1, 4-diene (D) penta-1, 3-diene
Solution: Since the compound on ozonolysis hyderolysis gives 1 mol of CO 2 and

butanoic acid it must be terminal alkyne pent-1-yne
CH3 – CH2 – CH2  CH  
 CH3 – CH2 – CHCOOH + CO2
i) H O 2
ii ) H 2 O
 (A)
Problem 4: When acetylene reacted with hydroxylic acid in presence of HgCl 2 the
product obtained is
(A) Methyl chloride (B) Acetaldehyde
(C) Vinyl chloride (D) Methanol
Solution: CH  CH + HCl   CH2 = CH – Cl

HgCl 2
 (C)
Problem 5: When propyne is treated with aqueous H2SO4 in presence of HgSO4, the
major product is
(A) Propanol (B) Propyl hydrogen sulphate
(C) Acetone (D) Propanol
Solution: CH3 – C  CH    CH3 – COCH3

H SO / HgSO 2 4 4
 (C)
Problem 6: Which one of the following does not of dissolve in conc. H 2SO4?
(A) CH3 – C = C – CH3 (B) CH3 – CH2 – C  CH
(C) CH  CH (D) CH2 = CH2
Solution: If CH  CH were to dissolve in H2SO4 a bisulphite salt of vinyl carbocation

H2C = C+H would be formed. The more s-character in the positively
charged ‘C’ less stable is the carbocation and less likely to be formed.
(C)
Problem 7: Which one of the following compounds will give in the presence of
peroxide a product different from that obtained in the absence of peroxide?
(A) 1-butane (B) 1-butene, HBr
(C) 2-butene, HCl (D) 2-butene, HBr
Solution: Peroixde effect is observed when unsymmetrical alkene is treated with

HBr only (and not with HCl and HI).
(B)
Problem 8: Which of the following alkene on acid catalysed hydration form 2-methyl
propan-2-ol.
(A) (CH3)2CH = CH2 (B) CH3 – CH = CH2
(C) CH3 – CH = CH – CH3 (D) CH3 – CH2 – CH = CH2
Solution: Addition of H2O occurs according to Markownikoff’s rule.

CH3 CH3

CH3 – C = CH2 + H2O  CH3 – C + CH3

H
CH3
 (A)
Problem 8: Which of the following compounds yields only one product on

monobromination?
(A) Neopentane (B) Toluene
(C) Phenol (D) Aniline
CH 3
|
Solution: CH3 – C  CH3 has twelve equivalent 1°H. Hence H forms only one
|
CH 3
product on monobromination.
(A)
Problem 9: Aqueous solution of the following compounds are electrolysed. Acetylene

gas is obtained from.
(A) Sodium fumarate (B) Sopdium maleate
(C) Sodium succinate (D) Both (A) and (B)
– –
Solution: CH – COO CH – COO
+
|| || + 2Na
– –
CH – COO CH – COO
–
CH – COO CH
|| || + 2CO2 + 2C at cathode
–
CH – COO CH
 (D)
Problem 10: Dehydration of butan-2-ol with conc. H2SO4 gives preferred product.
(A) but-1-ene (B) but-2-ene
(C) propene (D) ethane
H OH
| |
Solution: CH3 – C H – CH – CH3  
 CH3 – CH = CH – CH3 (80%)
H SO 2 4
+ CH3 – CH2 – CH = CH2 (20%)

This is in accordance with saytzeff rule.
 (B)
CH3 – C  C – CH3 

  ‘X’. What is X
2 NaNH
Problem 11:
(A) CH3CH2CH = CH2 (B) CH3CH2C  CH
(C) CH3 – CH = CH – CH3 (D) CH2 = C = CH – CH3
Solution: Isomerisation occurs, when 2-butyne is treated with NaNH2, it converts

into terminal alkyne (1-butyne).
 (B)
Problem 12: Identify the compound ‘Y’ in the following sequence of reactioin
HC  CH   X   Y

3 i) O
3 Zn / CH COOH
ii) H2 O / Zn
OH
(A) (B) OH
HO
O
OAc
(C) H3C (D)

CH3COOH
OAc
O OH
Solution: HC CH   
Ozonolysis
   HO
Re duction
O
 (A)
Problem 13: Dehydration of 1-butanol gives 2-butene as a major product, by which of

the following intermediate the compound 2-butene obtained
+ CH2
+ H3C C
(A) CH2 (B)
H3C
CH3
CH3
+ CH 3
(C) H C CH (D)
3 +
H3C CH2
Solution: +
CH 2

H3C OH 

H H3C

+
CH3   
1,2 hydride CH 2
+ Shift H3C
H3C CH
2° 1°
 (C)
Problem 14: The principal organic compound formed in the reaction
CH2 = CH(CH2)COOH + HBr  …………. is

Peroxide
CH3 – CH – (CH3)8COOH
(A) | (B) CH2 = CH(CH2)8COBr
Br
CH 2 –CH2(CH2)8COOH CH2 = CH(CH3)7 – CH – COOH

(C) | (D) |
Br Br
Solution: Follows the peroxide effect
 CH2 = CH(CH2)8COOH   CH 2 – CH2(CH2)8COOH

HBr
Peroxide
|
Br
 (C)
Problem 15: The compound most likely to decolourise a solution of potassium

permanganate is
(A) H2C CH2 (B)
CH3
(C) (D)
H3C CH3
Solution: It is a test for unsaturation. As benzene and naphthalene is also

unsaturated, but they are stabilized due to resonance, and thus does not
give Bayer’s test.
 (A)
7. Assignments
7.1 Subjective
LEVEL – I
O Cl
|| |
CH3 – C – CH2 – CH3   CH3 – C – CH2 – CH3   A. Identify A.
PCl5 NaNH2
1.
liq. NH3
|
Cl
2. The silver salt of an unknown alkyne contains 67.08% of silver. Assuming no

other group present, what is the structure of the alkyne?
3. How will you do the following conversion (give at least two methods)?
Br  D
4. Compound (A) C6H12 gives a positive test with bromine in carbon tetrachloride.
Reaction of (A) with alkaline KMnO4 yields only (B) which is the potassium salt of
an acid. Write down the structural formulae and IUPAC names of (A) and (B).
5. Compound A of m.f. C10H16 which cannot show geometrical isomerism, on

ozonolysis gave a symmetrical diketone B named 1,6-cyclodecadione. Identify A
and B.
6. OHC CHO
A 
Zn / O3
   B
Zn / O3
H2O H2O
CHO CHO
7. OH



H
Δ
Identify the mechanism of this dehydration reaction
8. OH


 an alkene. Identify the structure of the alkene.
H
Δ
Show all the intermediate steps.
9. It required 0.70 gms of a hydrocarbon (A) to react completely with Br 2 (2.0g). On

treatment of (A) with HBr it yielded monobromo alkane (B). The compound (B)
was obtained when (A) was treated with HBr in presence of peroxide. Write
down the structural formulae for (A) and (B) and explain the reactions involved.
10. Deduce the structural formula of the following arenes:

Compound A(C16H16) decolourizes both Br2 in CCl4 and cold aqueous KMnO4. It
adds an equimolar amount of H2. Oxidation with hot KMnO4 gives a dicarboxylic
acid, C6H4(COOH)2, having only one major monobromo substitution product.
What structural feature is uncertain ?
LEVEL – II
1. Br
Δ
   A 
( CH3 )2 NH
 B 
base
 C 
CH3I
 D 
Ag( OH )2
E
( excess) excess
Br
Give the products A, B, C, D and E
2. Find the products A, B, C

n – C13H27C  CH + n-BuLi  A
A + n – C8H17Br  B
B + H2    C
Lindlar' s Catalyst
Give the stereochemistry of C and how can you get the isomer of C?
3. i) Give the major products for the following reactions

a) 


H
C(CH3)3
OH
b) OH



H
Δ
c)
OH



H
CH3 Δ
CH3
CH3
d)
CH2 
Br2
H2O
1. BH3  THF
e) (CH3)2CHCH2CH = CH2  
2. H2 O 2 , H2 O
ii) Show the product and mechanism for the following reaction
CH = CH2

2 

H
4. i) Give the product for the following reaction

O
||
C
N  

HNO3
H2SO4
C
||
O
ii) Give the following conversions

a) CH3
CH3
Br
b) Br
Br Br
Br
c) OCH3
5. Compound (A) with M.W. 108 contained 88.89% C and 11.11% H. It gave a
white precipitate with ammoniacal silver nitrate. Complete hydrogenation of (A)
gave another compound (B) with molecular weight 112. Oxidation of (A) gave an
acid with equivalent weight 128. Decarboxylation of this acid gave cyclohexane.
Give structures of (A) and (B) and write the equation of the reactions involved.
6. An organic compound (A), C6H10 , on reduction first gives (B), C6H12, and finally
(C), C6H14. (A) on ozonolysis followed by hydrolysis gives two aldehydes (D),
C2H4O and (E) C2H2O2. Oxidation of (B) with acidified KMnO4 gives the acid (F),
C4H8O2. Determine the structures of the compounds (A) to (F).
7. Reaction of a hydrocarbon A of molecular formula, C10H20, with trioxygen and

then water gives two isomeric products, B and C, C5H10O. Oxidation of B leads
to an optically active acid D, C5H10O2, whereas oxidation of C leads to an acid E,
C4H8O2, which cannot be resolved into optically active forms. Reduction of C
gives F, C5H12O, dehydration of which followed by reaction with trioxygen and
then water, gives propanone as one of the products.
Deduce the structure of A and elucidate the reaction sequence.
8. An organic compound (A) of molecular formula C5H8 when treated with sodium in
liquid ammonia followed by reaction with n-propyl iodide yields (B), C8H14. (A)
gives a ketone (C), C5H10O, when treated with dilute H2SO4 and HgSO4. (B) on
oxidation with alkaline KMnO4 gives two isomeric acids (D) and (E), C4H8O2.
Give structure of compounds (A) to (E) with proper reasoning.
9. CH2OH


 . Identify A.
H
Δ
OH
10.
A B 

 
LiAlH4  C 
PCl5
 D 
alc. KOH
  E
HBr / H2O2
BBr3
2E  F
Identify A to F.
7.2 Objective
LEVEL – I
1. Ammonical AgNO3 reacts with acetylene to form:

(A) Silver acetate (B) Silver acetylide
(C) Silver formate (D) Silver metal
2. If 20cc of methane burnt using 50cc of oxygen the volume of the gases left after
cooling to room temperature:
(A) 60cc (B) 70cc
(C) 30cc (D) 50cc
3. On heating CH3COONa with sodalime the gas evolved will be

(A) C2H2 (B) CH4
(C) C2H6 (D) C2H4
4. The product obtained via oxymercuration (HgSO4 + H2SO4) of 1-butyne would be

H3C
CH3
(A) (B) H3C O
O
O
O + HCO 2H
H3C
(C) H3C + CH2O (D)
OH
5. A mixture of methane, ethylene, ethyne gases is passed through a Woulfe’s

bottle containing ammonical AgNO3. The gas not coming out from bottle is
(A) Methane (B) Ethyne
(C) Ethelene (D) All
6. Which of the following will have least hindered rotation about carbon-carbon
bond?
(A) Ethane (B) Ethylene
(C) Acetylene (D) Hexachloro ethane
7. Addition of one equivalent of bromine to 1, 3–pentadiene produces

(A) 1, 3–pentadiene produces (B) 4, 5–dibromo–2–pentene
(C) 3, 4–dibromopentene (D) 3, 4–dibromo–2–pentene
8. What is the chief product obtained when n–butane is treated with bromine in the
presence of light at 130°C?
(A) CH3 – CH2 – CH2 – CH2 – Br (B) CH3 – CH2 – CH – Br
|
CH3
(C) CH3 – CH – CH – Br CH3
| |
CH3 (D) H3C – C – CH2Br
|
CH3
9. Bromination of an-alkane as compared to chlorination proceeds

(A) at a slower rate
(B) at a faster rate
(C) with equal rates
(D) with equal or different rates depending upon the temperature
10. The product obtained on heating n-heptane with Cr2O3– Al2O3 at 600°C is
(A) Cyalohexane (B) Cyclohexane
(C) Benzene (D) Toluene
11. A sample of 1.79 mg of a compound of molar mass 90g mol–1 when treated with
CH3MgI releases 1.34 ml of a gas at STP. The number of active hydrogen in the
molecule is
(A) 1 (B) 2
(C) 3 (D) 4
12. 1 – Chlorobutane on reaction with alcoholic potash gives

(A) 1–butene (B) 1–butanol
(C) 2–butene (D) 2–butanol
13. The addition of Br2 to trans–2–butene produces

(A) (+) 2, 3 –dibromobutane (B) (-) 2, 3–dibromobutane
(C) rac –2, 3 –dibromobutane (D) meso–2. 3–dibromobutane
14. The ozonolysis of an olefin gives only propanone. The olefin is

(A) propene (B) but–1–ene
(C) but–2–ene (D) 2, 3–dimethylbut–2–ene
15. The treatment of CH3C = CH2

|
CH3
with NaIO4 or boiling KMnO4 produces
(A) CH3COCH3 + CH2O (B) CH3CHO + CH3CHO
(C) CH3COCH3 + CO2 (D) CH3COCH3 + HCOOH
16. Point out (A) in the given reaction sequence:

Δ
( A ) 3 2(B)  2CH3COOH  CO 2
O /H O
(A) (B)
(C) (D)
17. End product of the following sequence is:

2
CaO  C  ( A ) 
Heat
(c ) 
H2 O Hg
(C)
H2 SO4
(A) Ethanol (B) Ethyl hydrogen sulphate

(C) Ethanal (D) Ethylene glycol
18. 10 mL of a certain hydrocarbon require 25 mL of oxygen for complete

combustion and the volume of CO2 product is 20 mL. What is the formula of
hydrocarbon.
(A) C2H2 (B) C2H4
(C) CH4 (D) C2H6
19. Hydrogenation of the compound:

Me
Me Me
H
H
H
In the presence of poisoned palladium catalyst gives:
(A) An optically active compound (B) An optically inactive compound
(C) A racemic mixture (D) A diastereomeric mixture
20. Ozonolysis of will give
O
(A) 2 (B) O
O
O
(C) (D)
2
21. CH3 – CH – CH = CH2 + HBr  A (predominant), A is

|
CH 3
(A) CH3 – CH – CH – CH3 (B) CH3 – CH – CH2 – CH2Br
| | |
CH3 Br CH3
Br
(C) | (D) None is correct
CH3 – C – CH2 – CH3
|
CH3
22 Stability of CH3 – CH = CH – CH3 CH3 – C = C – CH3

(I) | |
. CH3 CH3
(II)
CH3 – C = CH2 CH3 – C = CH—CH3
| |
CH3 CH3
(III)
(IV)
In the increasing order is
(A) I  III  IV  II (B) I  II  III  IV
(C) IV  III  II  I (D) II  III  IV = I
23 CH3
|
H–C
||     A
alkaline KMnO 4
H–C
|
CH3
Which is true about this reaction?
(A) A is meso 1, 2-butan-di-ol formed by syn addition
(B) A is meso 1, 2-butan-di-ol fomred by anti addition
(C) A is a racemic mixture of d and l, 1, 2-butan-di-ol formed by anti addition
(D) A is a racemic mixture of d and l 1, 2-butan-di-ol formed by syn addition.
24. The treatment of C2H5MgI with water produces

(A) Methane (B) Ethane
(C) Ethanal (D) Ethanol
25. The order of reactivity of halogens towards halogenation of alkanes is

(A) F2 > Br2 > Cl2 (B) F2 > Cl2 > Br2
(C) Cl2 > F2 > Br2 (D) Cl2 > Br2 > F2
26. The chlorination of alkane involves

(A) Cl free radicals (B) Cl+ species
(C) Cl– species (D) CH3 free radicals
27. CH3
| CH3
H–C H Br
||  H
Br2
Br
C–H CH3
|
CH3
(A)
Which is true statement?
(A) A is formed by anti addition and is meso
(B) A is formed by syn addition and is meso

(C) A is formed by anti addition and is racemic
(D) A is formed by syn addition and is racemic
CH3
28. 2-butene + Br2  H Br and enantiomer. 2-butene is
Br H
CH3
(by anti addition)
(A) cis (B) trans
(C) both (D) none
(A) cis-2-butene I

HCO H
29. 3
HCO H
(B) trans-2-butene  3
 II
Correct statements are
(A) is racemic mixture by anti addition
(B) II is meso compound by anti addition
(C) I is meso compound by syn addition
(D) II is racemic compound by syn addition

30. B   
BH3 / THF
CH2   A
H3O
H2O2 / OH
A and B are
(A) (B)
both CH2OH both CH3
OH
(C) CH2OH, CH3
(D) CH3 CH2OH,
OH OH ,
LEVEL - II More than one choice

1.
H3 C CH 3 CH 3 H
C C C C
H H H CH 3
per acid per acid
A C
+ +
H /H2O H /H2O
B D
Which of the following statements is/are true :
(A) B is a single compound and optically inactive
(B) D is a single compound and optically inactive
(C) B is an equimolar mixture of two enantiomeric compounds
(D) D is an equimolar mixture of two enantiomeric compounds
2. Which of the following statements are correct on the basis of heat of combustion:
(A) Trans-2-hexene has less heat of combustion than 2-methyl-2-pentene

(B) Cis-2-pentene has higher heat of combustion than trans-2-pentene
(C) 1-hexene has higher heat of combustion than trans-2-hexene
(D) 2, 5-dimethyl hexane has higher heat of combustion than octane
3. O
C CH3 CH 2 CH3


This change can be carried out using:
(A) NH2 NH2, glycol/OH— (B) Zn(Hg)/conc. HCl
(C) P/HI (D) None of these
4. A + HBr  2-bromo-2, 3-dimethyl butane. Hence A can be:

CH3 CH3
CH2 CH3
(A) (B) H3C
H3C
CH3 CH3 OH
CH3
CH3 CH3
(C) CH2 (D)
H3C H3C CH3
OH
5. C4 H6 
H / Ni
 C4 H8 
2 O /H O
 CH3COOH
3 2
(A) (B)
Hence A and B are:

(A) CH3—CC—CH3, CH3CH=CH—CH3
(B) CH2=CHCH=CH2, CH3CH = CHCH3
(C)
, CH3CH = CHCH3
(D) None of these
6. The reaction
O
CH3  CH  CH  C2 H5 
C6 H5COOOH
 H3C HC CH C2H5
is called :
(A) Hydroxylation (B) Ozonolysis
(C) Prileschaiev’s reaction (D) Epoxidation
7. Which of the folowing on reductive ozonolysis give only glyoxal?
(A) Ethylene (B) Benzene
(C) Toluene (D) Acetylene
8. Aqueous solution of which of the following compounds is electrolysed, when acetylene
gas is obtained?
(A) Sodium fumerate (B) Sodium maleate
(C) Sodium acetate (D) Calcium carbide
9. Which gases are poisonous?

(A) Lewisite (B) Mustard
(C) Phosgene (D) MIC
10. Which of the following alkynes show acidic caracter?
(A) H – C  C – H (B) CH3 – C  C – H
C C H
(C) (D) CH3 – C  C – CH3
LEVEL - III Other Engg. Exams
1. Ethane is produced during the electrolysis of potassium salt of

(A) succinic acid (B) malonic acid
(C) acetic acid (D) fumaric acid
2. Which of the following statements is not true ?

(A) In ethane, staggered conformation is more stable than eclipsed conforamtion
(B) Cyclohexane exists in two conformations
(C) The boat conformation of cyclohexane is more stable than chair conformation.
(D) The boat and chair conformations of cyclohexane do not exist as independent
compounds
3. The compound with the highest boiling point is

(A) n-hexane (B) n-pentane
(C) 2, 2-dimethylpropane (D) 2-methylbutane
4. Marsh gas is
(A) methane (B) ethane
(C) propane (D) butane
5. Which of the following facts is correct ?

(A) C-D bond is slightly weaker than C-H bond
(B) C-D bond is slightly stronger than C-H bond
(C) both C – H and C – D bonds are equally strong
(D) Replacement of D in C – D by Cl is faster than the replacement of H in C- H.
6. The ozonolysis of 2, 4-dimethylpent –2-ene products

(A) two molecules of aldehydes
(B) two molecules of ketone
(C) one molecule of aldehyde and one molecule of ketone
(D) neither aldehyde nor ketone
7. The addition of HI in the presence of peroxide does not follow anti-Markovnikov’s rule
because
(A) HI bond is too strong to be broken homolytically
(B) I atom is not reactive enough to add on a double bond
(C) I combines with H to give back HI
(D) HI is a reducing agent
8. Identify the product in the following reaction:

heated with Cr2O3
n-heptane Product
supported on alumina at 6000C
(A) benzene (B) toluene
(C) xylene (D) cyclohexane
9. The treatment of ethylene with Baeyer’s reagent produces

(A) ethyl alcohol (B) acetaldehyde
(C) ethylene glycol (D) -hydroxyl acetaldehyde
10. The hydrolysis of Mg2C3 produces

(A) acetylene (B) propyne
(C) butyne (D) ethylene
11. Lindlar’s catalyst is

(A) Pt in ethanol (B) Ni in ethanol
(C) Pd with BaSO4 (D) Na in liquid NH3
12. The two hydrogen atoms in acetylene

(A) are acidic in nature
(B) are alkaline in nature
(C) are neutral in nature
(D) are acidic and alkaline in nature, respectively.
13. Which of the following is true?
(A) Acetylene is more reactive than ethylene to an electrophilic attack
(B) Acetylene is less reactive than ethylene to an electrophilic attack
(C) Acetylene may show more reactivity or less reactivity towards electrophilic attack
depending upon electrophilic reagent
(D) Acetylene and ethylene show identical reactivities towards an electrophilic attack
14. Which of the following orders regarding acid strength is correct ?

(A) CH3COOH > CH3CH2OH > CH  CH (B) CH3COOH > CH  CH > CH3CH2OH
(C) HC  CH > CH3COOH > CH3CH2OH (D) HC  CH > CH3CH2OH > CH3COOH
15. The product(s) obtained via oxymercuration (HgSO4 + H2SO4) of 1-butyne would be
(A) CH3CH2COCH3 (B) CH3CH2CH2CHO
(C) CH3CH2CHO + HCHO (D) CH3CH2COOH + HCOOH
LEVEL - IV
A Matrix-Match Type
1. From the given sets, match appropriately

Column – I Column – II
(A) H3C  H 2 O 2  HBr (p) Free radical mechanism
CH2
(B) (q) Elimination

Cl  Cl2  FeCl3
(C) H3C CH  HCl (r) Electrophilic substitution

(D) Br (s) Electrophilic addition
 NaNH 2
Br
2. With respect to the starting material, CH2 = CH – CH3, choose the type of reaction with
respect to the reagents.
Column – I Column – II
(A) KMnO4/H2O (p) Anti-Markonikov addition
(B) Br2 (q) Oxidative cleavage
(C) HBr/R2O2 (r) Syn addition
(D) Hot KMnO4/H+ (s) Anti-addition

3. Match Column I with Column II and select the correct answer :
Column – I (Reaction) Column – II (Reagent)
Br
(A) | (p) HBr
CH3 – CH = CH2  CH 3 CH  CH 3
(B) CH3- CH = CH2  CH3 – CH2 – CH2Br (q) NBS

(C) CH3 – CH = CH2  BrCH2 – CH = CH2 (r) Br2 / CCl4
(D) CH3 – CH = CH2  CH3 – CHBr – CH2Br (s) HBr (peroxide)
B Linked Comprehension Type
C1–3 : Paragraph for Questions Nos. 1 to 4

Chlorination of methane involves three steps: chain-initiating, chain-propagating and chain-
terminating.
Cl2 
Heat or light
2Cl Chain initiating
CH 4  Cl 
 CH3  HCl
Chain propagating
CH3  Cl2 
 CH3 Cl  Cl
When oxygen is passed through the reaction mixture, chlorination of methane slows down
temporarily
1. Chain-propagating steps
(A) consume reactive species and form another reactive species
(B) do not produce reactive species
(C) absorb energy and produce reactive species
(D) are not always the part of chain-reaction mechanism
2. Chain-terminating step may involve the formation of

(A) Chlorine (B) Methyl chloride
(C) Ethane (D) All the three
3. Although chlorination of methane is an exothermic, the reaction requires high

temperature because
(A) Activation energy is low (B) heat of reaction is negative
(C) Chain-initiating step is endothermic (D) Chain-terminating step is endothermic
4. Temporary slow down of chlorination of methane in presence of oxygen in due to the

formation of
(A) CH3OO which is highly unstable and decomposes easily
(B) CH3OO which is less reactive than CH3
(C) ClO which is highly reactive
(D) a diradical ClO
Hydrogenation of alkenes and alkynes takes place in presence of certain catalysts. In
Sabatier Senderen’s reaction, the addition of hydrogen takes place in presence of Raney
nickel catalyst. Platinum and palladium can also be used catalyst in these reactions.
These are heterogeneous catalyst and used in finely divided state. Experimentally, it is
observed that less crowded alkenes absorb H2 with faster rate. Controlled hydrogenation
of alkyne in presence of Lindlar’s catalyst yields cis product i.e., ‘cis’ alkene. Thus, in
presence of Lindlar’s catalyst ‘syn’ addition takes place. The relative rate of
hydrogenation follows the order
C  C   C C  C O  C6H6
Non-terminal alkynes are reduced in presence of Na or Li metal dissolved in liquid
ammonia. In this reaction, anti-addition of hydrogen results into the trans-product.
5. The relative rate of catalytic hydorgenation of following alkenes is :
(I) (II) (III) (IV)
(A) II > III> IV > I (B) I > IV > III > II

(C) III > IV > I > II (D) II > IV > I > III
6. CH3  C  C  CH3  H2 
Pd / CaCO3
Boiling Quinoline
 A
The product (A) will be
H H
(A) CH3CH2CH2CH3 (B) C C
H3C CH3
H3C H
(C) C C (D) CH3 – CH2 – CH = CH2
H CH3
7. In which of the following cases, the reaction is most exothermic?
(A) (B)
(C) (D)
8. The product of the following reaction is :

O
 H 2 
Pd / CaCO3
Boiling Quinoline

O O
(A) (B)
OH OH
(C) (D)
9. Powdered nickel is more effective than grannular nickel because :

(A) Surface area of powdered nickel is maximum
(B) Surface area of powdered nickel is minimum
(C) Powdered nickel increases the activation energy of the reaction
(D) Powdered nickel increases the intermolecular collision of reactant molecules

By virtue of its shape ‘s’ orbitals can attract electron density more than ‘p’ orbitals. More the ‘s’
character more is the electronegativity of the hybrid orbitals. Order of electronegativity of hybrid
orbitals is sp  sp2  sp3.
10. Which is acidic?
(A) H3C—C  C —CH3 (B) CH2 = CH2
(C) H3C — C  C—H (D) C2H6
11. Acetylene reacts with sodium hypochlorite to form
(A) vinyl chloride (B) dichloro acetylene
(C) sodium acetylide (D) chloro ethane
12. Acetylene reacts with sodium and methyl iodide and produces
(A) 2-butyne (B) 1-butyne
(C) 1-pentyne (D) 2-pentyne
13. 1-butyne and 2-butyne can be distinguished by
(A) Br2 in CCl4 (B) Tollen’s reagent
(C) Schiff’s reagent (D) 2, 4-DNP
9. Answers (Objective Problems)

LEVEL – I
1. (B) 2. (C)
3. (B) 4. (A)
5. (B) 6. (D)
7. (B) 8 (B)
9. (A) 10. (D)
11. (C) 12. (A)
13. (D) 14. (D)
15. (C) 16. (C)
17. (C) 18. (A)
19. (B) 20. (B)
21. (C) 22. (A)
23. (A) 24. (B)
25. (B) 26. (A)
27. (A) 28. (A)
29. (C), (D) 30. (D)
LEVEL – II
1. (B), (C) 2. (A), (B), (C)
3. (A), (B), (C) 4. (A), (B), (D)
5. (A), (B) 6. (C), (D)
7. (B), (D) 8. (A), (B), (D)
9. (A), (B), (C), (D) 10. (A), (B), (C)
LEVEL – III
1. (C) 2. (C)
3. (A) 4. (A)
5. (B) 6. (C)
7. (B) 8. (B)
9. (C) 10. (B)
11. (C) 12. (A)
13. (B) 14. (A)
15. (A)
SECTION – III
A B
Match the following Write-up
1 (A – p) 1. (A)
(B – r) 2. (D)
(C – s) 3. (C)
4. (B)
(D – q)
5. (A)
2. (A – r)
6. (B)
(B – s)
7. (B)
(C – p)
8. (A)
(D – q) 9. (A)
3. (A – p) 10. (C)
(B – s) 11. (C)
(C – q) 12. (A)
(D – r) 13. (B)

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RSM79Ph-IVHCCH1

2.1 Free Rotation about the Carbon-Carbon Single Bond: Conformations

H3C CH3 CH3

CH3 CH3 CH3

CH3 H3C CH3

H3C H3C CH3

CH3 CH3 CH3

H3C CH3 CH3

Exercise 2: Write the UPAC name for the following

2.2 Preparation of Alkanes

Reactions with No Change in Carbon Skeleton

1. Reduction of Alkyl Halides (RX, X = F, Cl, Br or I)

(Substitution of halogen by hydrogen)

c) RX + (n - C4H9)3 SnH  R-H + (n - C4H9)3 SnX

d) via organometallic compounds (Grignard Reagent). Alkyl halides react with

The net effect is replacement of X by H.

2. Hydrogenation of C=C (alkenes)

ii) How many hydrocarbon can be obtained by reacting the

with Na in presence of D.E.

Preparation of Alkanes with More C's than the Starting Compounds

Two R groups can be coupled by reacting RBr, RCl or RI with Na or K, yields of

2RX + 2Na  R-R + 2NaX

3. By heating a mixture of the sodium salt of a carboxylic acid and soda-lime

4. Kolbe's electrolytic method : A concentrated solution of the sodium or

2 RCOOK + 2H2O  R-R + 2CO2 + H2 + 2KOH

CH3CH2CH2-H  CH3CH2CH2 + H  Ho = + 98 k cal mol-1

CH2-CH-CH3  CH3  CHCH3 + H Ho = + 94 k cal mol-1

2.4 General Chemical Properties of the Alkanes

Halogenation: Chlorination may be brought about by photo irradiation, heat or catalysts,

The order of ease of substitution is

Tertiary Hydrogen > Secondary Hydrogen > Primary Hydrogen

Chlorination of isobutane at 300 oC gives a mixture of two isomeric monochlorides:

RCl + NaI   RI + NaCl

This reaction is possible because sodium iodide is soluble in methanol or acetone,

(Reactivity of X2: F2 > Cl2 > Br2; I2 does not react)

The mechanism of methane chlorination is:

Initiation Step: Cl : Cl 

The required enthalpy comes from ultraviolet (uv) light or heat.

i) H3C : H + Cl  H3C + H : Cl H = - 4KJ mol-1 (rate determining)

ii) H3C + Cl : Cl  H3C : Cl + Cl H = - 96 KJ mol-1

The sum of the two propagation steps in the overall reaction,

CH4 + Cl2  CH3Cl + HCl H = - 100 KJ mol-1

Cl + Cl  Cl2 ; H3C + Cl  CH3 : Cl

H3C + CH3  H3C : CH3

2. Reactivity of H : The order of reactivity of H is 3o > 2o > 1o.

CH3 Cl2 / h CH3

CH3 CH3 H3C

CH3CH2CH2CH3  CH3CH2CH2CH2Cl + CH3CH2CHClCH3

n  butylchloride no.of1o H reactivityof1o H

In bromination of isobutane at 127oC,

Isobutylbromide no.of 1o H reactivity of 1o H

Hence, tert-butyl bromide happens to be the exclusive product (over 99%).

Alkenes (olefins) contains the structural unit

CH3CH = CH2 H2C CH2

The C=C consists of a  bond and a  bond, in a plane at right 

H3C CH3 H CH3

CH2 = CH — CH2 = CH CH2 —

The following examples illustrate how these names are employed

CH2 = CH — Br CH2 = CH — CH2 Cl

3.2 The (E) - (Z) System for Designating Alkene Diastereomers

Higher priorityBr H Higher priorityBr H

Example: The IUPAC name for

3.3 Relative Stabilities of Alkenes