ALKENE

 Intro duct ion :

Alkenes are hydrocarbons with carbon-carbon double bonds, Alkenes are sometimes called olefins, a term
derived from olefiant gas, meaning 'oil forming gas'. Aleknes are among the most important industrial compounds
and many alkenes are also found in plants and many alkenes are also found in plants and animals. Ethylene
is the largest-volume industrial organic compound, used to make polyethylene and a variety of other industrial
and consumer chemicals. Alkenes polymerises to give many important polymers.
 Str ucture a nd bondi ng i n Alkene s :
(a) Alkenes are unsaturated hydrocarbons having at least one double bond.
(b) They are represented by general foumula (G.F.) C n H 2n (one double bond)
(c) In Ethene C = C bond length is 1.34 Å
(d) Its bond energy is 146 kcal. mol –1
(e) The hybridization of (C = C) alkenic carbon is sp 2
(f) The  e – cloud is present above and below the plane of s-bonded skeleton.
(g) They are also known as olefins since ethene, the first member of the homologous series forms oily
liquid substance when treated with halogens.
(h) Compounds may exist as conjugated polyenes or as cumulated polyenes or as isolated polyenes

1.34Å
117.2° 1.10Å H H H H
(b) C— C C— C
H H H H
121.2°
(a)

Note : That angle a < b since repulsion due to  electrons (double bond - single bond repulsion > single
bond - single bond repulsion according to VSEPR theory.
 IUPAC Nomenclature of alkene s a nd alkadi ene s :
Table - I
S.No. Compound Name Type
1. (CH 3 ) 2 C = CH 2 2–Methylpropene Alkene
2. CH 3 –CH=CH–CH 2 –CH=CH 2 Hexa–1, 4–diene Isolated diene
3. CH 2 =CH–CH = CH 2 Buta–1, 3–diene Conjugated diene
4. CH 3 –CH=C=CH–CH 3 Penta–2, 3–diene Cumulated diene

Cl
5. 1 2 3 4 5 6 7 6–Chlorohept–3–ene Alkene
CH3–CH–CH=CH–CH
2 2–CH–CH3

1 2 3 4 5
6. CH2=CH–CH=C–CH3 4–methoxypenta–1, 3–diene Conjugated diene
OCH3
1 2 3
7. CH2=CH–CH–C CH 3–Ethynylpenta–1, 4–diene Isolated diene
4
CH
5
CH2
 S.No. Compound Name Type

CH3 C2H5
6 5 4 3 2 1
8. CH3–CH–C
2 = C–CH2–CH3 3–Ethyl–4–methylhex–3–ene Alkene

1
6
2 CH3
9. 5 3 2, 3–Dimethylcyclohex–1–ene Cycloalkene
4
CH3

10. CH 2 = C = CH 2 Propadiene Cumulated diene

11. CH 2 = C = O Ethenone Alkene

12. Methylenecyclopentane Alkene

13. Cyclopentylethene Alkene

14. 3, 7, 11–trimethyldodeca– Isolated triene

1, 6, 10–triene

Ex. Write IUPAC names of :

CH3
CH3
(a) (b)

S o l . (a) 2, 3–Dimethylcyclohexene; (b) 1–(2–butenyl) cyclohex–1–ene

Ex. Give the structure for each of the following
(a) 4–Methyl–1, 3–hexadiene ;(b) 1–Isopropenylcyclopentene

S o l . (a) ; (b)

 Isomerism :
Alkenes show chain, Ring chain or functional, Position, Geometrical isomerism and optical isomerism.
For more details refer to isomerism provided to you in study material.

Ex. What is relation between CH 3 CH CH 2 , CH2 CH2 ?

CH2

S o l . Ring chain isomerism

Ex. (a) CH 3 CH 2 CH CH 2 (b) CH 3 —CH CH—CH 3 (c) CH3 C CH2 (d) CH2 CH2

CH3 CH2 CH2

Define relations between a,b,c,d ?

S o l . a and b – Position isomerism ; a and c – Chain isomerism
a and d – Ring chain isomerism ; b also show Geometrical isomerism

CH3 CH3 CH3 H

C C C C
H H H CH3

cis–2–butene trans–2–butene

Ex. How many minimum carbon atom persent in optically active alkene?

S o l . 6C, H
CH3 CH2 C* CH CH2
CH3

3–Methyl–1–Pentene
 Preparat ion of Alkene s :
(1) From Alcohols : Alkene s can be prepared from monohydric alcohols or alkanols by the loss of
H 2 O and the react ion is know n as dehydrat ion react ion.

 
C C     C C + H2O
Alkene
H OH

Alcohol
The dehydration can be carried with Al 2 O 3 or with mineral acid upon heating.
(a) Dehydration with Al 2 O 3 : Ethene is prepared by heating ethanol with Al 2 O 3 at 620 K.
Al2 O 3
CH 3 —CH 2 —OH 
620 K

 CH 2 CH 2 +H 2 O

Ethanol Ethene
(b) Dehydrat ion w it h mi neral acid : Alcohols upon heat i ng w ith conc. H 2 SO 4 form alkene s
and the reaction is called acidic dehydration.
95 % H 2 SO 4
CH 3 —CH 2 —OH 
440 K
 CH 2 CH 2 +H 2 O

Ethanol Ethene

OH
60% H 2 SO 4
CH3 CH CH3 
373 K
 CH —CH
3 CH 2 + H 2 O

Propan–2–ol Propene

CH3 CH3
30% H 2 SO 4
CH3 C CH3  CH3 C CH2 + H2O
363 K
OH

2–Methylpropan–2–ol 2–Methylpropene
 From the above reactions, it is clear that the order of acidic dehydration in different alcohols is

Tertiary > Secondary > Primary

Cycloalkenes can be prepared in the same way by the dehydration of cycloalkanols.

OH
H PO / heat
Example : 
3 4

 + H2O

Cyclohexanol Cyclohexene

CH3 CH3 CH3 CH2

H 3 PO 4 / heat

 + +
OH
(major)

Regioselectivity of  elimination is governed by Zaitsev's Rule.

Machanism of React ion: T he acidic dehydration of alcohol proceeds through the formation of a
carbocation intermediate and is explained as follows :
Step I : Alcohol being a Lewis base accepts a proton (H +) from the acid in a reversible step as follows:

..  
..


.. H + H  CH3 CH2 O H
CH3 CH2 O
H
Ethanol (From acid) Protonated ethano
Step II : Due to presence of positive charge on electronegative oxygen, its electron accepting tendency
increases. As a result C – O bond becomes weak and cleaves as follows :


.. 
Slow
CH3 CH2 O H  CH 3 — CH 2 + H 2 O
H
Ethyl carbocation
T his is a slow and is regarded as rate determi ni ng step.
Step III : Carbocation is unstable in nature and loses a H + and changes into ethene in a fast step as follows:
 Fast
H—CH 2 — C H 2   CH 2 CH 2 + H +

Ethene
Note: Dehydration of secondary and tert alcohol is best carried out by using dil. H 2 SO 4 . Since alkenes
produced from those alcohols have a tendency to form polymers under the influence of concentrated acid.

Saytzeff Rule : When two possible alkenes are obtained by the elimination reaction than that alkene
will be in good yield, containing maximum number of alkyl group on double bonded C–atoms

OH
H 2 SO 4
CH3 CH2 CH CH3 
 C H 3— C H C H — C H 3+ C H 3— C H 2— C H CH2

2–butanol main product 1–butene

2–butene 80% 20%
 H 2 SO 4
CH 3 —CH 2 —CH 2 —CH 2 —OH   CH 3 —CH CH—CH 3 + CH 3 CH 2 CH CH 2

1–butanol 2–butene80% 1–butene 20%
Main product
Mecha nism : Acid catalyzed dehydration of alkanols proceeds via the format ion of more stable
carbonium ion.

  
CH 3 CH 2 CH 2 —CH 2 — O —H+ H  CH 3 CH 2 CH 2 CH 2 OH 2


 
CH 3 CH 2 CH 2 CH 2 OH 2  CH 3 CH 2 CH 2 — CH 2  H 2 O
Primary Carbonium ion
H H H H
 
CH3 C C C H Re arrangement by
  CH3 C C C H
1, 2 hydride ion shift

H H H H H H
1 0 Carbonium 20 Carbonium more stable
H H CH3 CH CH CH3

CH3 C C C H
E lim ination of
 2– butene (major Product)
a proton

H H H CH3 CH2 CH CH2

1–butene (minor product)
(Saytzeff rule)
(2) From Alkyl halide (By dehydrohalogenat ion): Removal of HX from a substrate by alcoholic
KOH or NaNH 2
KOH ( Alc.) 
RCH 2 CH 2 X  
 RCH CH 2
 HX

KOH ( Alc.) 
Example : CH3 CH2 CH CH3  
 CH 3 CH CH—CH 3 + CH 3 CH 2 CH CH 2
 HX

X
(Saytzeff rule)
The ease of dehydrohalogenation show the order

For alkyl group tertiary > secondary > primary

For halogen in halide Iodide > Bromide > Chloride  flouride

It is si ngle step and synchronous proce ss. Removal of proton, the format ion of mult iple bond
between C and C and the release of the leaving group X take place simultaneously.
(E 2 mechanism)

H H H
C2H5O+CH3 C C H CH3 C C H +C2H5OH + Br




Example :
H Br H


Rate of reaction  [CH 3 CH 2 CH 2 Br] [C 2 H 5 O]
 KOH ( Alc)
Example : CH 3 CH 2 CH 2 CH 2 Br   CH 3 CH 2 CH  CH 2
1  Bu te n e

Example : KOH (Alc)

CH3CH2CHCH3  CH 3 CH  CHCH 3
2  Bute n e (major )
Br
Primary and secondary alkyl halides undergo elimination reaction by E 2 mechanism. E 1 elimination
reactions are shown by tertiary alkyl halides which are capable of producing stable (tert) Carbonium
ion on show ionization.
CH3 CH3

CH3 C Cl              CH3 C+ Cl
CH3 CH3

CH3

CH3

HO +H CH2 C
   CH2 C + H2O
CH3
CH3
E 2 mechanism : Those alkyl halides which do not give Stable Carbonium ion on ionization show
E 2 elimination.

HO
Base
H
 
CH3 CH2 CH CH2 CH3 CH2 CH CH2 + H2O + Cl




Cl
(A) Dehalogenation of vicinal dihalides :
There are two types of dihalides namely gem (or geminal) dihalides in which the two halogen atoms
are attached to the same carbon atom and vicinal dihalides in which the two halogen atoms are
attached to the adjacent carbon atoms.
Dehalogenation of vicinal dihalides can be effected either by NaI in acetone or zinc in presence of
acetic acid or ethanol.
 General Reaction
Br
NaI
(i) –C–C– 
or Zn,CH 3 COOH
 C=C
Br
Br
••
Mech. –C–C– Zn –C––C–   –C=C–+ZnBr2
Br Br

Zn dust
(ii) CH 3 –CHBr–CH 2 Br 
 CH 3 COOH or 
 CH 3 –CH=CH 2
 C H OH as solvent 
2 5

Mech.
With NaI in acetone :

I X••
–C–C–  C=C + IX
X
It involves an antielimination of halogen atoms
Remarks :
(i) Both are E 2 elimination.
(ii) Both are stereospecific antielimination.
NaI
Example : CH 3 –CHBr–CHBr–CH 3 
Acetone
 CH 3 –CH=CH–CH 3

Ex. Identify the product in the following reactions :

CH3 CH3
H Br H Br
(a) NaI / acetone
  (b) NaI / acetone
H Br
Br H  

CH3 CH3
H CH3 CH3
H
S o l . (a) ; (b)
H3C H H CH3

(B) From gem dihalide : Higher alkene obtained

CH 3 CH X 2 + 2Zn + X 2 CHCH 3  CH 3 —CH CH—CH 3 + ZnX 2

(3) By Pyrolysis of e ster :

400  500  C
CH3 C O CH2 CH R   CH 3 COOH + CH 2 CHR

O  H

Hoffma nn's Rule : Le ss substituted or less stable alkene is major product.

 
Example : 
CH3 C O CH CH2 CH3  CH3 COOH + CH CH2 CH3 + CH CH CH3
O CH3 CH2 CH3
(Major) (Minor)
In the reaction to form an alkene a -hydrogen from alkyl ester is at tracted by oxygen atom of
keto group & Hoffmann's alkene will be the major product.
(4) By Pyrolysis of tetra alkyl ammonium ion :

CH3 H CH3

 OH
CH3 N CH2 CH2  CH3 N + CH2 CH2 + H2O
CH3 CH3

Example :
CH3

CH3 N CH CH2 CH3  CH CH2 CH3

CH3 CH3 CH2 CH2


  —OH
CH3 N CH CH2 CH3  1° more stable major product
—H2O
CH3
CH3 CH3 

CH3 N CH CH CH3  CH CH CH3
CH3 CH3 CH3 minor product
2° less stable
 CH3
 
 CH2 CH CH3 (minor)
 —OH
Example : CH3 N CH2 CH2 CH3 
—H O 2

CH2 CH3 CH2 CH2 (major)

(a) In this reaction –hydrogen of tetra-alkyl ammonium ion is attracted by a base and alkene
is formed.
(b) In this react ion i ntermediate is carbanion.So yield of product depends on stabilit y of
carbanion.
(c) In this reaction Hoffmann's Rule is followed.
(6) By Kolbe's method:
Electrolysis of potassium or sodium salt of saturated dicarboxylic acid gives alkene.

CH2COONa electrolysis CH2 + 2CO2 + NaOH + H2


CH2COONa CH2 At Cathode

At Anode

Electrolysis
CH3 CH COONa   CH3 CH+2CO2 + NaOH + H2
CH2COONa CH2 At Cathode
At Anode

CH3 CHCOONa electrolysis

 CH3 CH+2CO2 + NaOH + H2
CH3 CHCOONa At Cathode
CH3 CH
At Anode
(7) Pyrolysis of Tri alkyl ami ne Oxide : (Cope React ion)

CH3 CH3
  150
R CH2 CH2 N O   R—CH CH 2 + N OH
CH3 CH3

(8) Hydrogenat ion of alkyne :

By par t ial reduct ion of Alkyne s -
(a) By cataly t ic Hydrogenat ion of Alkyne s i n pre sence of poisoned catalyst (A Syn
Addition of Hydrogen : Synthesis of cis-Alkenes : This is per formed by)
(i) Lindlar's catalyst : Metallic palladium deposited on calcium carbonate conditioned with lead
acetate and quinoline.
(ii) P- 2 catalyst (Ni 2 B nickel boride)
H 2 Pd/CaCO 3
(Lindlar 's catalyst)
R R
General react ion R–CC–R   C=C
quinoline
H H
Mecha nism of hydrogenat ion :

C= C
(1) (2) H H H H
H – H + – C C – + H – H    H H –C = C– H H  

metal surface desorption

adsorption
 Steps : The reactant alkyne molecules and hydrogen molecules get adsorbed at the surface of metal
catalyst. It is chemical adsorption (chemisorption).
In this state, the reactants lie ver y close to each other and so the hydrogen atoms star t forming
bond w ith carbon. Two hydrogen atoms are added to t wo triply bonded carbon atoms from the
same side of  bond and a cis or syn addit ion pro duct is formed. T he product alkene now
escapes away from the surface of the catalyst. Quinoline occupies the metal surface inhibiting further
reduction to alkanes Quinoline therefore is called catalyst poison and such palladium is called
dectivated catalyst or poisoned catalyst.
Example :
H2/Ni2B(P-2) CH3CH2 CH2CH3
or H2/Pd/CaCO3
CH3CH2C CCH2CH3       C= C
(syn addition)
3-Hexyne H H
(Z)-3-Hexene
(cis-3-Hexene)
(97%)

(b) Birch Reduct ion : (Anti addit ion of hydrogen : synthe sis of trans-alkene s)

R H
Na/Li
 General react ion R–C C–R   
Liq. NH
C= C
3

H R

Mechanism : Reagents Na (or Li, K) + liq NH3 Na++ e– (sollvated electron)

• R R
Na H – NH2 H
R – C  R  C= C  C= C
R R

•
Na

R H H2N–H R
NaNH2 + C= C H

 C= C
H R Na
R
(~100%)
(trans alkene)

Na / NH 3 (  )
Example : : CH 3 –CH 2 –CC–CH 2 –CH 3   CH3CH2 H
C= C
H CH2CH3
trans
hex-3-ene

Note : This process of reduction is not eligible when terminal alkynes are taken (R–CCH) because
terminal alkyne s form sodium salt with Na metal.
CH 3 –CCH + Na/NH 3  CH 3 –CC–Na + + [H] +
Ex. Identify the reagent for following synthesis

O
O
?
CH2–CC–CH2CH3  
cis-Jasmone
(A)
Sol. H 2 /Lindlar's catalyst
H
A  2
Lindlar ' s catalyst
 cis - Jasmone
Ex. Identify the product in the following reaction :

Na / NH 3
 
CH2–CCCH3

Sol.
CH2 H
C= C
H CH3

(9) Wittig Reaction :

The aldehydes and ketones are converted into alkenes by using a special class of compounds called
phosphor us ylide s, also called Wit t ig reagent s.
The Triphenyl group of phosphorane has a strong tendency to pull oxygen atom of the aldehyde
or ketone via a cyclic transition state formi ng an alkene.
R" R"
C=O C–O
R" R" R" R'
 R–C – PPh3  C=C + Ph3P = O

R–C–PPh3 R" R'
R'
R' ylide
(R, R', R" and R''' may be hydrogen or any alkyl group)

Me
.. C= O Me
e.g. Ph3P: + CH3 – Br    [Ph3P –CH3] Br    Ph3P –CH2] Me
 Bu–Li 
     Ph3P=O + C = CH2
Me
Methyltriphenyl Ylide
phosphorium salt Product alkene

 Physical Proper t ie s of Alkene s / Hydrocarbons :

Physical proper t ie s Homologus series Isomers

1. Physical state C 1 – C 3 gases
C 4 – C 20 liquids
> C 2 0 : solids
2. Dipolemoment () cis > trans
3. Polarity _ cis > trans (for C ab =C ab type of alkenes)
4. Melting point increases with M.W. trans > cis
(due to more packing capacity
5. Boiling point increases with M.W. cis > trans
# branching decreases B.P.
C
C–C=C < C – C = C – C
Polarity increases, boiling point increases
6. Solubility Practically insoluble in cis > trans
water but fairly soluble Polarity increases, solubility in polar
in nonpolar solvents solvents increases.
like benzene petroleum
ether, etc.
7. Stability trans > cis (cis isomers has more
Vander Waals repulsion
 Chemical Proper t ie s :
Alkenes are more reactive than alkane this is because -
(a) The  electrons of double bond are located much far from the carbon nuclei and are thus less
firmly bound to them.
(b)  bond is weaker than  bond and more easily broken.
The reactivity order for alkenes -
CH 2 CH 2 > R—CH CH 2 > R 2C CH 2  RCH CHR > R 2C CHR > R 2C CR 2
(Trans < Cis)
The reactivity order of alkenes has been delt in terms of heat of hydrogenation of alkene, more is the
heat of hydrogenation (H = –ve), more is the reactivity, the reactivity of alkene is however also
related to
(i) Steric hinderence (ii) Hyperconjugation (iii) Heat of Combustion.
All four butenes may be compared, since all give the same products on combustion viz. 4CO 2+4H 2 O
Alkene s give t he fol low i ng t ype of react ions :
(a) Addition reaction (b) Oxidation reaction. (c) Substitution reaction.
(d) Polymerization Reaction. (e) Isomerisation

A l k en e H ea t o f c o m b u s t io n (k J/m o l ) H ea t o f h y d r o g en a t io n (k c a l /m o l )

1-Butene 2719 30.3

Isobutene 2703 27.2

Cis-2-butene 2712 28.6

trans-2-butene 2707 27.6

(A) Addition Reaction :

[ A 1 ] free radical addit ion :
 Addition of H 2 :
Ni,Pt or Pd
R—CH CH 2 +H 2   R—CH —CH + Heat of Hydrogenation.
2 3
N o t e : (a) Reaction is exothermic, It is called heat of hydrogenation.

1 1
(b) Stability of alkene  
heat of hydrogenation reactivity of alkene with H 2

(c) The process is used to obtain vegetable (saturated fats) ghee from hydrogenation of oil.
(B) [ A 2 ] Electroph i lic addit ion react ions :
Because of the presence of >C C< bond in molecules, alkenes generally take part in the addition
react ions.

C C
C C + AB 
A B
Alkene Attacking molecule Addition product
 From mechanism point of view, the addition in alkenes is generally electrophi lic i n nature which
means that attacking reagent which carries the initial attack is an electrophile (E+ ). This is quite
expected also as there is high electron density in the double bond. The mechanism proceeds in two
steps.
Step I : The –electron cloud of the double bond causes the polarisation of the attacking molecule
(E–Nu) which cleaves to release the electrophile ( E  ) for the attack. The double bond simultaneously
undergoes electromeric effect and the attack by the electrophile is accomplished in slow step (also
called rate determi ni ng step) to form a carbocat ion i ntermediate.

( Slow )
C C 
Rate determining step (RDS)


Addition product

Step II : The nucleophile (: Nu – ) released in the slow step combines with the carbocation to give
the desired addition product in the fast step.
1. Addition of Halogen : It is a electrophilic addition reaction.

X X
R CH CH2 + X2 R CH CH2
(Vicinal halides)

N o t e : (a) Reactivity order of halogen is : Cl 2 > Br 2 > I 2

(b) Addition of F 2 is exothermic reaction so it is difficult to control.
(c) The addition of Br 2 on alkenes provides a useful test for unsaturation in molecule.The brown
colour of the bromine being rapidly discharged. Thus decolarization of 5% Br 2 in CCl 4 by a
compound suggest unsaturation in it. Colourless dibromo compound is formed.
(d) I 2 reacts slowly with alkenes to form Vicinal di-iodides which are unstable and eliminated I 2
molecule ver y readily to give original alkene due to large size of Iodine they overlap.

CH 3 —CH CH 2 + I 2  CH3 CH CH2

I I
Unstable

 Mechanism : It is interesting to note that product which is mainly formed as a result of addition
is trans in nature whereas the cis isomer is obtained in relatively smaller proportions. Since
carbocation intermediate is planar (sp 2 hybridised), both cis and trans addition products must be
formed almost in equal proportions. The trans product can be justified in case a cyclic ion is formed
by the initial electrophile attack.

+ – ( Slow )
CH2 = CH2+ Br—Br    CH2 CH2
Br
(Halonium ion)
The attack of Br – ion on the cyclic ion takes place from the side opposite to side where bromine
atom is present in order to minimise steric hindrance.
  H2C ( Fast )
Br + Br  Br H2C
H2C
CH2 Br
1,2,–Dibromoethane,
For 2, 3-dimethylbut-2-ene :
Step I :

H3C CH3 CH3

CH3
H3C ••
+ ••Br••
••
H3C CH3 • + CH3
•• •Br••
+ ••Br•• Bromonium ion Bromide ion
• •
– Br
•
••
•

A bromine molecule becomes polarized as it approaches the alkene. The polarized bromine molecule
transfers a positive bromine atom (with six electrons in its valance shell) to the alkene resulting in
the formaiton of bromonium ion.
Step II :
H3C ••
H3C CH3 •
Br
• •
•

H3C H3C
CH3 •• C—C
C—C + ••Br••
•• •• CH3
• •
• + •Br •
•Br•• CH3
Bromonium ion Bromide ion vic-dibromide

aq.NaCl
Ex. CH 2  CH 2 + Br 2   Products, what are the products?
Ethylene
Br
Sol. 
Br
CH2 CH2

Br
Cl
CH2 CH2 + Br2  CH2 CH2 Cl
CH2 CH2
Br
Br
OH2 OH
H2O –H
CH2 CH2 CH2 CH2
Br Br

Br Br
Nal
CH2 CH2 + Br CH2 CH2 I
Similarly CH 2 CH 2 + Br 2
NaNO3
Br CH2 CH2Br + BrCH2CH2 NO3
2. Addition of halogen acid :

X
R—CH CH—R + HX  R CH2 CH R

X
R—CH CH 2 + HX  R CH CH3
N o t e : (i) The order of reactivity of hydrogen halide is : HI > HBr > HCl > HF
(ii) Their addition is an example of electrophilic addition.
(iii) Addit ion on alkene proceeds via the format ion of more stable carbonium ion.
(iv) Addition of HX on unsymmetrical alkenes (R—CH CH 2 ) takes place according to
Markownikoff's rule.

 MARKOWNIKOFF'S RULE :

(a) First Rule : When molecule of a HX add up on unsymmetrical unsaturated hydrocarbon, the
halogen atom goes to the unsaturated carbon atom bearing lesser number of hydrogen atoms.

CH3 CH CH2 + HX   CH3 CH CH2

H

Mechanism : It is electrophilic addition and is illustrated by the action of HCl to propene.

 
CH3 CH CH2 + H Cl 
Slow
 CH 3 — C H — CH 3  Cl –
Secondary carbocation


–
Cl + CH3 CH CH3
Fast
  CH3 CH CH3

Cl
2–Chloropropane

Primary carbocation (CH 3 —CH 2 — CH 2 ) is formed but only in very small proportion since it is less
stable than the secondary carbocation. Markownikff's rule can also be stated as :
T he electroph i lic addit ion to unsymmetrical alkene s always occur s t hrough t he format ion
of a more stable carbocat ion i ntermediate.
(b) Second Rule : In the addition of HX to vinyl halide and analogous compounds, the halogen
attaches itself to the carbon atom, on which the halogen atom is already present.

CH 2 CH—Cl+HCl   CH3 CH Cl

Cl
Ethylidene chloride

 Mechanism :  
.. .. ..
CH2 CH Cl
.. :  CH 2 CH ..:
Cl

Cl 
  
..  ..

H Cl
CH3 CH Cl  CH2 CH Cl ..

In vinyl chloride two effects operate simultaneously in opposite direction-

(i) Inductive effect – electron attracting (-I) effect of chlorine.
(ii) Resonance effect – electron pair releasing (+R) effect of chlorine.
The resonance effect is much more than the -I effect of Chlorine at the time of attack.This creates
centre s of +ve and –ve charges.
          
All polar reagents of the general structure Y Z (such as H X, H OH H SO3H, X OH) add on
unsymmetrical unsaturated compound in accordance with Markownikoff's rules. Such additions are
called normal Markownikoff's rule, where as additions in the opposite manner are reffered to as
abnormal or a nt imarkow nikoff's addit ions.

 ANTI MARKONIFF'S RULE OR PEROXIDE EFFECT OR KHARASCH RULE :

(i) In the presence of oxygen of peroxides the addition of HBr on unsaturated unsymmetrical
compound takes place contrary to Markownikoff's rule. This is called peroxide effect and is
due to the difference in the mechanism of the addition.
(ii) In the normal Markownikoff's addition the mechanism is ionic.
(iii) In the presence of peroxide the addition of HBr takes place via free radicals.

HBr
CH3 CH CH3 Markownikoff's addition.
Br
CH3 CH CH2 Isopropyl bromide
HBr
CH3 CH2—CH—Br
2 Anti Markownikoff's addition
R O O R
n–Propyl bromide

 Mechanism :
(i) Chain initiation -
(a) R—O—O—R  2RO •
(b) HBr + RO •  ROH + Br •
(ii) Chai n propagat ion

. HBr
.
CH3 CH CH2Br  CH3CH2CH2Br + Br
. 2° free radical more stable (major)
CH3 CH CH2 + Br
Br Br
. HBr
.
CH3 CH CH2 CH3CHCH3 + Br
1° free radical less stable

(iii) Chai n termi nat ion :

R    R  R—R

R    Br  R—Br


Br  Br  Br—Br

Ex. Why HCl and HI do not give antimarkownikoff products in the presence of peroxides.?
S o l . (a) T he H—Cl bond is stronger than H—Br.
(b) The H-I bond is weaker than H—Br bond. It is broken by the alkoxy free radicals obtained
from peroxides, but the addition of iodine atom on alkene is endothermic as compared to
Br atom therefore iodine atoms so formed combine with each other to yield iodine.
3. Addition of Hypohalous acid (or X 2 /H 2 O, or HOX) : It is a electrophilic addition and follows
Markownikoff's rule.

  
Slow –
Cl Cl + H2C CH2  CH2 CH2 + Cl
Cl
Carbocation

 .. (Fast) –H–
.. H CH2
CH2 CH2 + H O CH2 CH2 CH2
Cl Cl H O
.. H Cl OH

Ethylene chlorohydrin

In the fast step, there is competition between Cl – ion and H 2 O molecule to act as nucleophile but
H 2 O is a better nucleophile.

Re activity order is HO C l > HO B r > HO I

4. Addition of H 2 SO 4 : Alkene react with conc. H 2 SO 4 to produce alkyl hydrogen sulphate. Which
gives alcohols on hydrolyses.This reaction used to seprate alkene from a mixture of alkane and
alkene.

OSO3H OH
HO
CH3 CH CH2+ HOSOH
3
 CH3 CH CH3  CH3 CH CH3 + H2SO4 2

Isopropyl alcohol


C2H4 + H2SO4

CH2 CH2 + H2SO4  CH3CH2HSO4

H2O
C2H5 OH + H2SO4

Ethyl hydrogen sulphate give ethylene when heated 430-440K while ethanol is obtained on boiling
it with water.
5. Addition of water (Hydration of alkenes) : Propene and higher alkenes react with water in
the pre sence of acid to form alcohol. T his react ion is know n as the hydrat ion react ion .
Intermediate in this reaction is carbo cation, so rearrangement will take place.

+
H
CH3—CH=CH2 + H2O CH3—CH=CH3
(i)
OH
Propene Propan-2-ol

OH
CH3 C CH2 + H2O  H
(ii)  CH3 C CH3
CH3 CH3
2–Methylpropene 2-Methylpropan-2-ol

 Mechanism :

CH3 CH CH2 + H+ 
(Slow )
 CH3 CH CH3
Carbocation (2°)
  .. ( Fast ) –H 
.. H   CH3 CH CH3  CH3 CH CH3
CH3 CH CH3 + H O
H ..
O H O H


Propan-2-ol

Cl NO
 
6. Addit ion of NOCl (Ti lden CH3 CH CH2 + NOCl  CH3 CH CH
reaga nt) :
Propylene nitrosochloride
7. Hydroborat ion : It obe ys markoni'koff's rule.Diborane readi ly react s with alkenes giving trialkyl
boranes. The reaction is called hydroboration.
+ – +  –
2R CH CH2 + B2H6  2(R CH2 CH2) BH2

 R CH CH2

R CH CH2
(R CH2 CH2)3B  2(R CH2 CH2)2 BH
Trialkylborane
BH 3 does not exist or stable as monomer so a solvent THF (tetra hydro furane) is used.

 H  
Example : 3CH3 CH CH2 + B H THF ( C H 3— C H 2— C H 2) 3B
 
H
BHR 2 also can be taken.
 
Example : CH CH CH2 + BHR2  CH3 CH2 CH2 BR2
3

H2O/H+
(CH3 CH2 CH2)3B 3CH3 CH2 CH3 + H3BO3
Tripropyl Borane Propane


H2O2/OH
CH3 CH2 CH2 OH
Propanol
(1° alcohal)
Cl NH2
CH3 CH2 CH2 NH2 + NaCl + HBO
3 3
NaOH
(1° amine)
Propanamine

8. Oxymercurat ion – demercurat ion : Mercuric acetate i n tetrahydro furan (THF) is treated with
an alkene.The addition product on reduction with sodium Boro hydride in aqueous NaOH solution
gives alcohol. It follows the markonikoff's rule.
C H 3— C H C H 2  CH3 CH CH3
OH
(i) (AcO) 2 Hg/H 2 O (Mercuric acetate) or (CH 3 COO) 2 Hg/H 2 O
(ii) NaBH 4 / NaOH
 Mechanism :

CH3 COO H2 o —
Hg  CH 3 —COO + CH 3 —COOHg + (Electrophile)
CH3 COO
 + +
CH3 CH CH2 + HgOOCCH3 CH3 CH CH2
:HgOOCCH3

H
  :O H

:
CH3 CH CH2 H2O H O H OH
   +
HgOOCCH3 –H3O
CH3 CH CH2 CH3 CH CH2

(cyclic cation) HgOOCCH3 HgOOCCH3

(Oximercuration)


NaBH /NaOH
OH

4
CH3 CH CH2 + CH3COOHg+

H
(Product)
Note : Intermediate is c yclic cat ion so t heir is no rear ra ngement.

OH
+
H /H2O
CH3 C CH2 CH3 with rearrangement
markownikoff's rule
CH3
OH
CH3 CH CH CH2  (i)BH3/THF
CH3 CH CH CH2 without rearrangement
(ii)H O / –OH
CH3
2 2
anti-markownikoff's rule
CH3 CH3
Cl
HCl
CH3 C CH2 CH3 with rearrangememt
markonikoff's rule
CH3
OH
(i) (AcO)2Hg/H2O
CH3 CH CH CH2 without rearrangement
(ii) NaBH4/NaOH
markownikoff's rule
CH3 H
HBr
CH3 CH CH CH2 without rearrangement
Peroxide
anti - markownikoff's rule
CH3 H Br

9. Hydroformylat ion or Oxo react ion : Alkene s react with Carbon monoxide and hydrogen at
100 – 150°C temperature and high pressure (200 atm) in the presence of Cobalt catalyst to produce
an aldehyde.It does not follows markonikoff's rule.
The net reaction is the addition of a H–atom to one of the Olefinic bond and a formyl (–CHO)
group to the other.

Co/150°C R CH2 CH2 CHO

R CH CH2 + CO + H2 high pressure
R CH CH3
CHO
10. Alkenylation (Addition of alkene) In presence of H 2 SO 4 or H 3 PO 4 at 80°C dimerisation of
isobutylene take place gives two isomer of octene.

CH3 CH3 CH3 CH3 CH3

H2SO4, 80°C
2CH3 C CH2  CH2 C CH2 C CH3 + CH3 C CH C CH3
CH3 CH3

Mechanism :

CH3 CH3
CH3 C CH2 + HCH3 C CH3


CH3 CH3 CH3 CH3

CH3 C CH2 +  C CH3  CH3 C CH2 C CH3

CH3  CH3
–H

CH3 CH3 CH3 CH3

CH2 C CH2 C CH3 CH3 C CH C CH3
CH3 CH3

11. Addition of Carbene : The addition of carbene to alkene is always carried by diazomethane
CH 2 N 2
Carbene group obtained from diazomethane is added to alkene and give cycloalkanes.

CH 2 CH 2 + CH 2 N 2  CH2 CH2 + N2
CH2

CH3 CH.. CH2 +:CH2 CH3 CH CH2

CH2
Since : CH 2 is an electrophile (neutral) and there is more electron density on double bond so first
attack of :CH 2 will be at double bond.
   
12. Addition of HCN: CH3 CH CH2 + HCN  CH3 CH CH3
CN

(B) OXIDATION RE ACTION :

Alkenes are easily oxidised by oxidising agents. Oxidising agents attack on double bond and product
formed during oxidation depends on oxidising agents.
(1) alkene on combustion gives CO 2 and H 2 O
3n
C n H 2n + O 2  nCO 2 + nH 2 O
2

3n
One mole of alkene requires moles of O 2 for complete combustion.
2
Ex : 90 mL of oxygen is required for complete combustion of unsatuarated 20 mL gaseous hydrocarbon,
hydrocarbon is ?
S o l . Following two formulae can be used for solution of the above asked question.
Volume of Hydrocarbon 2
 (for Alkene)
Volume of O 2 3n

Volume of Hydrocarbon 2
 (for Alkyne)
Volume of O 2 3n  1

By putting the values in above formulae we can find the hydrocarbon for which n is natural number.

20 2
 n = 3 So hydrocarbon is Propene [C 3 H 6 ].
90 3n

Ex. How many mole of oxygen is required for complete combustion of 1 mole of Alkene.

S o l . 2C n H 2 n  3nO 2  2nCO 2  2nH 2 O

keeping in mind, the above equation.

 for 2 mole of Alkene, 3n mole of O 2 is required for combustion.

3n
 for 1 mole of Alkene, mole of O 2 is required for combustion.
2
= 1.5n mole of O 2
Ex. 30 mL mixture of ethylene and Butylene is burnt in presence of oxygen then 150 mL of oxygen
is required, what is the volume of Ethylene & Butylene in mixture.
S o l . Let the volume of C 2 H 4 = x mL
So volume of Butylene = (30–x) mL

For C 2 H 4 C 2 H 4  3O 2  2C    2H 2 O

from equation
 for 1 volume C 2 H 4 , 3 volume of O 2 is required.
 for x mL vol. of C 2 H 4 , 3x ml volume of O 2 is required.
For C 4 H 8 C 4 H 8 + 6O 2  4CO 2 + 4H 2 O
 for 1 volume C 4 H 8 , 6 volume of O 2 is required.
 for (30–x) mL " " , 6 (30–x) mL of O 2 is required.
Total volume of O 2 = 3x + 6 (30–x) mL = 150 mL(Given)
x = 10
 Volume of C 2 H 4 in mixture is 10 mL
 Volume of C 2 H 4 in mixture is 20 mL
(2) Ozonolysis : (A test for unsaturation in molecule)
(i) The addition of ozone on the double bonds and subsequent a reductive hydrolysis of the
ozonide formed is termed as ozonolysis.
(ii) When ozone is passed through an alkene in an inert solvent, it adds across the double bond
to form an ozonide. Ozonide s are explosive compound the y are not isolated.
(iii) On warming with Zn and H 2 O, ozonides cleave at the site of the double bond, the products
are carbonyl compound (aldehyde or ketone) depending on the nature of the alkene.
 Example : Ozonolysis
CH3 C CH CH3 
 CH3 C O + CHCHO
3

CH3 CH3

(iv) Ozonolysis of alkenes helps in locating the position of double bond in an alkene. It can be
achieved by joining together the carbon atoms of the two carbonyl compounds formed as the
products of ozonolysis with double bond.

H H
1 2 3 4
Example : CH3 C O + O C CH3  CH3 CH CH CH3

Ethanal But-2-ene

H H
1 2 3 4
Example : H C O + O C CH2 CH3  CH2 CH CH2 CH3

Methanal Propanal But-1-ene

CH3 CH3 CH3 CH3

Example : CH3 C O + O C CH3  CH3 C C CH3

Propanone 2,3–Dimethyl but–2–ene

It may be noted that reaction with bromine water or Baeyer's reagent detects the presence of double
bond (or unsaturation) in an alkene while ozonolysis helps in locating the position of the double
bond. In an reduction of ozonide by LiAlH 4 or NaBH 4 gives corresponding alcohols.

O
LiAlH4
R' CH CH R"  R'CH2OH + R"CH2OH
O O (Alcohols)

(3) Hydroxylation : Oxidation of carbon-carbon double bond to C C is known as hydroxylation.

OH OH

(a) Oxidation by Baeyer's reagent (A test for unsaturation) : Alkenes on passing through dilute
alkaline 1% cold KMnO4 (i.e., Baeyer's reagent) decolourise the pink colour of KMnO4 and gives
brown ppt MnO 2 and glycol.

OH –
C C + H2O + [O] 
KMnO  C C Glycol
4

OH OH (cis–addition)

R CH R CH O O R CH OH
(b) By OsO 4 : H2O
+ OsO4  Os  + H2OsO4
R CH R CH O O R CH OH
cis–addition
 O OH
(c) By peracid :  HCOOH  H2O
>C C < + H C O O H   >C C<   >C C<
O HO H
trans glycol
(4) Epoxidation :
(a) Alkenes reacts with oxygen in the presence of Ag catalyst at 250°–400° C to form epoxide.

O OH
1 Ag H2 O
CH 2  O 2 
CH 2   CH2 CH2
  CH2 CH2 (anti addition)
2
OH
(b) Prile schiaev react ion: When an alkene is treated with perbezoic acid an epoxide is formed.
Such an epoxidation is known as Prileschiave reactions.
RCH CH 2 + C 6 H 5 COOOH  R CH
O + C6H5COOH
CH2
Epoxide
Emmons have found that perbenzoic oxy trifluoroacetic acid (CF 3 COO 2 H) is a very good reagent
for epoxidation and hydroxylation.
Syn addition Syn addition
Meso compound Racemic mixture
cis alkene trans alkene
Anti addition Anti addition
Racemic mixture Meso compound

Syn addition on alkene  H 2 , O 2 , Baeyer ' s reagent, OSO 4 / H 2 O

Anti addition on alkene  X 2 , HOX, RCOOH / H 2 O, Ag 2 O / H 2 O
Example :
CH3 CH3
(i) Br2
H Br Br H
CH3 H Anti addition +
Br H H Br
C
CH3 Racemic mixture CH3
C
CH3 H CH3
D2
cis–alkene Syn addition H D
H D
CH3
Meso compound

(ii) CH3 CH3

Baeyer's
OH H H OH
CH3 H Reagent +
Syn addition H OH OH H
C
CH3 Racemic mixture CH3
C
H CH3 CH3
RCOOOH/H2O
trans-alkene Anti addition H OH
H OH

CH3
Meso compound
(5) Oxidat ion by strong oxidisi ng agent (Oxidat ive cleavage) : T he alkene s themselve s are readi ly
oxidised to acid or ketone by means of acid permagnate or acid dichromate.If HCOOH is formed,
it further oxidized to CO 2 and H 2O. Keep it in mind that no further oxidation of ketones will takes
place.

CH 2 2[O ]
CH 2 +4[O] 2HCOOH   2CO 2 + H 2 O

CH 3 CH 5[O ]
CH 2   CH 3 COOH+CO 2 +H 2 O
4[O ]
CH 3 CH CHCH 3   2CH 3 COOH

CH3 CH3
4[O ] C O + CO2 + H2O
C CH2 
CH3 CH3

(6) Oxidat ion w it h retent ion of Carbon-Carbon bond - (Waker proce ss) :

2PdCl
CH 2 CH 2 +H 2 O 2 
CuC l
 CH 3 CHO
2

(C) SUBSTITUTION REACTION (Allylic substitution) :

When alkenes are treated with Cl 2 or Br 2 at high temp., one of their allylic hydrogen is replaced
by halogen atom. Allylic position is the carbon adjacent to one of the unsaturated carbon atoms.It
is free radical substitution.
0
CH 3 —CH CH 2 + Cl 2 500 C
   ClCH 2 —CH CH 2 + HCl

Allyl chloride
(3-Chloro-1-propene)
N-Bromosuccinimide (NBS) is an important reagent used for allylic bromination and benzlic substitution.

O O
CH3 CH CH2 + CH2 C CH2 C
NBr  NH + Br CH2 CH CH2
CH2 C CH2 C
(NBS)
O O

Substitution reaction is not given by ethene.

CH3 CH2 Br
Example : (i) NBS
 


(ii) NBS Br
   
H . Br
CH3 CH3 CH3

3° more stable
(D) POLYMERIZATION :
(i) Two or more than two molecules of same compound unit with each other to form a long
chai n molecule w ith same empirical formula. T his long chain molecule havi ng repeati ng
structural units called polymer, and the starting simple molecule as monomer and process is
called addition polymerization.
 (ii) Molecular weight of polymer is simple multiple of monomer.
(iii) Polymerization can be carried out by free radical or ionic mechanism.
(iv) The presence of oxygen initiates free radical mechanism.
(v) Addition polymerization can also be carried out by ionic mechanism by using Ziegler - Natta
Catalyst s (R 3 Al+TiZCl 4 )

Name of Str ucture of Str ucture of Proper t ie s Use s Proper t ie s

polymer monomer Polymer
1. Polyvinyl CH 2 =C H– Cl –( H2C–HC –
)n Piliable Used in handbag,
chloride Cl (easily moulded) raincoats, vinyl
(PVC) flooring, good elec-
trical insulator
for wires

2. Polytetrafluor- F 2 C= CF 2 –( F2C–CF2 –
)n Flexible and inert For making non-stick
ethylene or to solvents, boiling utensils coating
Teflon (PTFE) acids,even aquaregia
stable upto 598K.

CH3
3. Natural rubber CH2=CH–C=CH2 Wa xy and non-elast ic Used as raw material
isoprene
for making vulcanised
rubber which is strong
and elastic vulcanised
rubber is used in
making tyres hose,
pipes etc.

4. Orlon acrylonitrile –( H2C–HC)–n Fibrous Used in making

CN Fabrics

CH3 CH3
5. Poly methyl CH2=C –CH2–C
COOCH3 C=O
methacrylate
Methyl methacrylate OCH3 n
(PMMA)

(E) ISOMERISATION :
Alkene on heating to 500° to 700 °C or on heating in presence of catalyst [AlCl 3 or Al 2 (SO 4 ) 3 ]
undergo isomerisation.
Catalyst
CH 3 CH 2 —CH CH 2   CH 3 —CH CH—CH 3 + CH3 C CH2

CH3
1–Butene 2–Butene Isobutylene
 Uses :
(a) In plastic formation.
(b) In oxy ethylene welding
(c) As food preservatives and ripening fruits.
(d) As general anaesthetic (C 2 H 4 with 10% O 2 )
(e) In preparation of mustard gas

CH2 CH2 CH2Cl CH2Cl

+ S2Cl2 + +S
CH2 CH2 CH2 S CH2

2,2' or (, ') dichloro diethyl-sulphide

(mustard gas)
 Laboratory test of alkene :

Fu nc tio n a l
Re a g en t O bs e r va t ion Re a cti on Re m a rk s
Gro u p

(1 ) Baye r's
alk. KMnO4
Pink colour
CH2 =CH2 +H2O+O
Reagent alk . dil. CH2 –CH2 Dihydroxylation
disappears
cold KMnO 4
OH OH

Br2+ CH2 = CH2 CH2 –CH2

C= C Red colour
(2) Br 2/H 2O Dibrominaiton
de colourises Br Br
Whit e ppt.

Zn/H2O
(3) O 3 (ozone) C=O CH2 =CH2 + O3 2HCHO Ozonolysis
Compounds

: DIENES :
Dienes are the unsaturated hydrocarbons with carbon-carbon double bonds in their molecules. These
are represented by the general formula C n H 2n 2 which means that they are isomeric with alkyness
(functional isomers). However, their proper ties are quite different from those of alkynes. Depending
upon the relative positions of the two double bond, dienes are classified in three types :
Isolated dienes or non conjugated dienes : In an isolated diene, the two double bonds are
separated by more than one single bond. For example,

CH3
1 2 3 4 5
1 2 3 4 5
CH2 CH CH2 CH CH2 CH2 CH CH CH CH2

Penta–1,4–diene 3–Methylpenta–1, 4–diene

Cunjugated dienes : In a conjugated diene, the two double bonds are present in the conjugated
or alternate position and are separated by a single bond.

CH3
1 2 3 4
1 2 3 4 5
CH2 CH CH CH2 CH2 C CH CH CH3

Buta-1,3-diene 2-Methylpenta-1,3-diene
 Commulate dienes : In this case, the two double bonds in the molecules are present at adjacent
positions. For example,
1 2 3 1 2 3 4
CH2 C CH2 CH2 C CH CH3
Propa-1,2–diene Buta–1, 2–diene
 Comparison of relat ive stabi lit ie s of isolated a nd conjugated diene s :
Resonance Theory : The relative stabilities of the two types dienes can also be justifid on the
basis of the theory of resonance. Penta-1,3-diene (conjugated diene) is a hybrid of the following
contributing structures.

   
CH2 CH CH CH CH3  CH2 CH CH CH CH3  CH2 CH CH CH CH3
The delocalisation of -electron charge because of resonanace decreases the energy of the molecule
or increases its stability.
Penta-1, 4–diene (isolated diene) has only two contributing structures.
1 2 3 4 5 1 2 3 4 5
CH2 CH CH2 CH CH2  CH2 CH CH2 CH CH2
(I) (II)
Since the carbon atom C 3 is not involved in any resonance, the contributing structures are less in
number are compared to the conjugated diene. The isolated diene is, therefore, less stable than a
conjugated diene.
 Proper t ie s of Conjugated Diene s :
The properties of the isolated dienes are similar to those of simple alkene but those of conjugated
dienes are somewhtat modified because of delocalisation of the -electron charge. However, they also
participate in the addition reactions. The important chemical characteristics of the conjugated dienes
are briefly discussed.
1. Addition Reaction : Conjugated or 1,3–dienes take part in the addition reactions which can
proceed by electrophilic as well as free radical mechanism depending upon the nature of the
attacking reagent and the reaction conditions.
(A) Electrophilic Addit ion React ions : The electrophilic addition is illustrated by the attack of halogen
and halogen acid on buta–1,3–diene, a conjugated diene.
(a) Addition of halogen : If one mole of halogen attacks per mole of the diene, two types
of addition products are formed. There are 1, 2 and 1, 4 addition products. For example,
Br Br
1 2 3 4
CH2 CH CH CH2
3,4–Dibromobut–1–ene
1 2 3 4 Br2
CH2 CH CH CH2 (1,2–Addition)
Buta–1, 3 diene Br Br
1 2 3 4
CH2 CH CH CH2
1,4–Dibromobut–2–ene
(1,4–Addition)
1, 2–addition is a normal addition in which one mole of halogen has been added to one of the
double bond. But 1, 4-addition is somewhat unexpected.
 Mechanism : The addition is electrophilic in nature and the halogen molecule (bromine) provides
the electrophilie for the attack.
    
CH2 CH CH CH2 + Br Br  CH2 CH CH CH2Br + Br
Buta-1, 3-diene Carbocation (2°)
The 2° carbocation get stablised by resonance as follows –
 
CH2 CH CH CH2 Br  CH2 CH CH CH2 Br

I II

The attack of Br ion on carbocation ( I and II )

Br

CH2 CH CH CH2 Br CH2 CH CH CH2 Br

Br (1,2–Addition)

CH2 CH CH CH2 Br CH2 CH CH CH2
Br Br
1,4–addition (Main product)
(b) Addition of H – X :
HBr
CH 2 CH—CH CH 2  ?
 Mechanism : The addition is electrophilic in nature as H  ion is the electrophile.
  
CH2 CH CH CH2 + H Br  CH2 CH CH CH3+ Br–

Carbocation (2°)
The carbocation gets resonance stabilised as follows :
 
CH2 CH CH CH3 CH2 CH CH CH3

(I) (II)
The attack of Br –ion on the carbocation (I) gives 1,2-addition product whereas the attack on the
carbocation (II) yields 1,4-addition product.

Br–+ CH2 CH CH CH3  CH2 CH CH CH3
Br
1,2–Addition product

Br–+ CH2 CH CH CH3  CH2 CH CH CH3
Br
1,4–Addition product
(B) Free Radical Addit ion React ion : T he addit ion to conjugated diene s can also proceed by free
radical mechanism provided it is carried in the presence of a suitable reagent which can help in
forming a free radical. However, the addition also yields 1,2 and 1,4 addition products. The free
radical addition is illustratated by the attack of bromotrichloromethane (BrCCl 3 ) on buta–1,3–diene
in the presence of an organic peroxide such as benzoyl peroxide.

1 2 3 4 4 3 2 1 4 3 2 1
Benzoyl
CH2 CH CH CH2 + BrCCl3   Cl3CCH2CH CH CH2 + Cl3CCH2 CH CH CH2
peroxide

Br
Buta–1,3–diene Bromotri-
chloromethane
 Mechanism : The mechanism of addition is free radical in nature which is initiated by benzoyl free
radical. It is explained in the following steps :
Step I Generation of free radical
 
C 6 H 5 CO—O—O—COC 6 H 5 Homolysis
  C 6 H 5 —CO— O  O —COC 6 H 5

 
C 6 H 5 —C O— O  C 6 H 5 + CO 2

 
C 6 H 5  BrCCl 3 C 6 H 5 —Br + CCl 3

Trichloromethyl free radical

Step II Attack of free radical on buta-1, 3-diene
 
C Cl 3 +CH 2 CH—CH CH 2  Cl 3 C—CH 2 — C H —CH CH 2

Free radical (secondary)

The free radical gets resonance stabilised
 
Cl 3 C—CH 2 — C H —CH CH 2  Cl 3 C—CH 2 —CH CH— C H 2

Step III Change of free radical into addition product


The free radicals take up Br from the attacking reagent to give the desired addition products.
i.e. 1,2 and 1,4 addition products.
.
BrCCl3 + Cl3C CH2 CH CH CH2  Cl3C CH2 CH CH CH2
Br
(1,2-Addition product)
.
BrCCl3 + Cl3C CH2 CH CH CH2  Cl3C CH2 CH CH CH2
Br
(1,4–Addition product)

2. Cyclo-Addition Reaction (Diel Alder Reactions) :

Cyclo-addition reactions are one of the most important reactions of conjugated dienes. Cyclo-addition involves
the combination between a conjugated diene (4-electron system) and a compound containing a double bond
(2-electron system) called dienophile which means a diene loving or attracting molecule. As a result, a six
membered ring gets formed and the reaction is therefore known as cyclo-addition reaction. It is quite often
termed as (4 +2) cyclo-addition reaction because four 4-electron system adds to a two 2 electron system.
The reactions of this type are known as : Diel Alder Reaction.
The addition product is called Diel Alder Adduct. For example.

CH2 CH2
HC CH2 HC CH2
HC +  HC CH2
CH2
CH2 CH2

Buta–1,3–diene Ethene Cyclohexene (Diel Alder adduct)

 CH2 CH2
HC CH CHO HC CH CHO
HC +  HC CH2
CH2
CH2 CH2

Buta–1,3–diene Propenal 3-cyclohexene carbaldehyde

(Acrolein)
Ex. The densit y of a hydrocarbon at N.T.P. 2.5 gram/litre. What is hydrocarbon?
S o l . Density of 1 litre hydrocarbon = 2.5 gram/litre
 molecular weight of hydrocarbon = 2.5 x 22.4 = 56
After molecular weight , we calculate the molecular formula.
C n H 2 n 2 = molecular weight (Alkane) or 14n+2 = molecular weight

C nH2n = molecular weight (alkene) or 14n = molecular weight

C n H 2 n 2 C n H 2 n 2 = molecular weight (Alkyne) or 14n–2 = molecular weight

with the help of above three formulae, we can ident ify the given hydrocarbon
14n = 56 (Alkene)  Hydrocarbon is C 4 H 8 (Butene).
n = 4
Volume of hydrocarbon will be given and volume of O 2 for complete combustion will also be
given.
What is hydrocarbon is to be asked ?
The above question may be solved w ith the help of followi ng three formulae.

Volumeof H.C. 2
Formula No. 1  (for Alkane)
Volume of O 2 3n+ 1

Volume of H.C. 2
Formula No. 2  (for Alkene)
Volume of O 2 3n

Volume of H.C. 2
Formula No. 3  (for Alkyne)
Volume of O 2 3n– 1

Ex. How much propanol is required for dehydration to get 2.24 litre of Propene at N.T.P. if yield is
100%.
S o l . C 3 H 8 O  H 2 SO 4  C 3 H 6  H 2 O  H 2 SO 4
Molecular weight of propanol = 60
from the equation given above we can see that from dehydration of 1 mole or 60 gram of
propanol we get 1 mole (22.4lit.) of propene as product.
 22.4 litre of C 3 H 6 can be get from dehydration of 60 g of propanol.
60
 1 litre of propene can be get from dehydration of 22.4 g of propanol

60
 2.24 litre of propene can be get from dehydration of 22.4 x2.24 g of propanol

Ans. = 6 g