ALKE NES

(Olefins) general molecular formula: CnH2n

Nomenclature
The -ane suffix of alkane is replaced by –ene
IUPAC Nomenclature

2 3 5
4 5 4
1 2 3
1
3 5 2 4
1
2-Pentene 4-M ethyl-1-pentene 2-Ethyl-1-pentene

1 CH3
4 6 8 1 2 3 4
5 5 6
CH3CH CHCH2C CH3
2 3 7
CH3
2,5-Dimethyl-2-octene 5,5-Dimethyl-2-hexene
 CH3 CH3
4 3 2 1
CH3CH CHCH2Cl CH3C CHCH2CH CH3
1 2 3 4 5 6
1-Chloro-2-butene 2,5-Dimethyl-2-hexene

OH has higher priority then double bond:

OH
1
4 2 6 2
OH
5 3 1 5 3
4
3-Penten-1-ol Cyclohex-3-en-1-ol
In Cycloalkenes

3 1
2 4 5 2

1 5 3
4
6
3-M ethylcyclohexene 1-M ethylcyclopentene

1 Cl Cl
6 2 5 4 3
3 1 2
5
4
3,5-Dimethylcyclohexene 4,4-Dichlorocyclopentene
If there is more than one double bond in a compound

1 2 3 4 5
CH2 CH CH2CH CH2 1,4-Pentadiene

1 2 3 4
CH2 CH CH CH2 1,3-Butadiene

4
3 5 2 4
1 6 7
2 6 3 5
1

1-Ethyl-1,4-cyclohexadiene 6-M ethyl-2,4-heptadiene

*Common names (Historical)

CH2 CH Vinyl Group CH2 CH Cl Vinyl Chloride

CH2 CH CH2 Allyl Group CH2 CH CH2 OH Allyl Alcohol

3 2CH3 1
CH2 CH2 CH3CH CH2 CH3C CH2
Common: Ethylene Propylene Isobutylene
IUPAC: (Ethene) (Propene) (2-M ethylpropene)

or also commo
Isobutene
Cis-Trans Isomerism
2-Butene can exist in two isomeric forms:

These are configurational isomers

CH3 CH3 CH3 H

C C C C
H H H CH3
Cis-2-butene Trans-2-butene

Cl Cl Cl H H H
1 2 1 2 3 4
C C C C
H H H Cl 1
2 5 6
Cis-1,2-dichloroethene Trans-1,2-dichloroethene Cis-3-hexene

2 4
6
1 3 5
Trans-3-hexene
The Z–E system (Geometrical isomers)
We examine the two groups attached to one carbon atom of the double bond and
decide which has higher priority then we repeat that operation at the other carbon.
* If the higher-priority groups are on the same side, use the prefix
Z-(Zusammen; together).
* If the higher-priority groups are on opposite sides use
E-(Entgegen; opposite). Cl F Cl H
1 2 1 2
CHCl= CHF C C C C
H H H F
(Z)-1-Chloro-2-fluoroethene (E)-1-Chloro-2-fluoroethene

H F H Cl
2 1 2 1
C C C C
Br Cl Br F
(Z)-2-Bromo-1-chloro-1-fluoroethene (E)-2-Bromo-1-chloro-1-fluoroethene

I > Br > Cl > S > F > O > N > C > H

Priority
4 5 1 4 5

2 3
2 3
1 Br Br
(Z)-3-Bromo-2-pentene (E)-3-Bromo-2-pentene
 Preparation of Alkenes
0

(1) CH3CH2 OH + Conc. H2SO 4

160-170 C
CH2 CH2

(2) CH3CH2CH2Br + KOH/ EtOH CH3CH CH2 + KBr + H2O

Propyl bromide ethanol
MeOH
CH3CH2CHBr2 + Zn ZnBr2 + CH3CH CH2
(3)
Propyldiene bromide
Br
methanol Propylene

MeOH
CH3CHCH2Br + Zn ZnBr2 + CH3CH CH2
Propylene bromide Propylene

1 2-dibromopropane
(4) Wurtz synthesis:

1,1-dibromopropane
 CHEMICAL REACTIONS OF ALKENES
I – Hydrogenation (Reduction) of Alkenes (Addition of H2)

H2/ Pt
CH2 CH2 CH3 CH3 (Catalytic Hydrogenation)

H2/ Pt

Cyclohexene Cyclohexane
CH3 CH3
H2/ Pt
H

CH3 CH3
H
Cis-1,2-Dimethylcyclohexane 1,2-Dimethylcyclohexane
 II – Electrophilic Addition of Alkenes
(A) Addition of hydrogen halides (hydrohalogenation) HX

Ether
CH2 CH2 + HBr CH3 CH2Br Ethyl Bromide
Cl

+ HCl Ether Chlorocyclopentane

Mechanism (Ionic Reaction)

+ -
X
CH2 CH2 + H X CH2 CH3 XCH2 CH3
Ethene Hydrogen Halide Carbocation Ethyl Halide

HBr BrCH2CH3
Ethyl Bromide
For Unsymmetrical alkane (Markovnikov's Rule)

CH3 CH3 CH3

HBr
C CH2 CH3 C Br CH CH2Br
start
Ether Not
CH3 CH3 CH3
2-M ethyl-1-propene 2-Bromo-2-methylpropane
I

Not I
HI

1-Butene 2-Iodobutane

HBr
Br
CH3 CH3

Markovnikov's Rule
In the addition of HX to an alkene, the H+ adds to the carbon atom of the double
bond that already has the greater number of hydrogen atoms.
Br
CH2 CH CH3 + HBr CH2 CH CH3
3
Mechanism (Ionic reaction)
H -
X
+ X
CH2 CH CH3 + H X CH2 CH CH3 CH3 CH CH3
M ore stable carbocation

H - X
+ X
CH2 CH CH3 + H X CH2 CH CH3 CH2 CH2 CH3
Less stable carbocation
{Not by this way} Not formed
 Radical Addition to Alkenes
Addition of hydrogen halide in presence of peroxide this reaction is
under free radical condition (Anti Markovnikov's Rule).

8bl lazm H 3nd R O O R

Peroxide
2 RO

c ele 3ndo H aktrRO + H Br R OH + Br

ama hoon
H 3ala el c ele feh Br Br
H 28l CH3 CH2 CH2 CH3 CH2 CH3
H Br 0
CH3 CH CH2 1 Radical (less stable)
Peroxide

CH3 CH CH2Br CH3 CH2 CH2Br

Anti Markovnikov's 0
2 Radical (M ore stable) M ajor products

Fhma eno el H lazm t9eer 4 wo lao double bo bt9eer 2 H

(B) Addition of water to Alkenes: (Hydration)
Acid-catalyzed hydration
tert = carbon atta to 3 carb
The reaction follows Markovnikov's rule
CH3 CH3
C CH2 + H2SO4/ H2O CH3 C CH3
CH3 OH
2-M ethyl-1-propene tert-Butyl Alcohol
OH
H2O/ H+
CH3CH2CH CH2 CH3CH2CH CH3
1-Butene 2-Butanol

H2SO4/ H2O
OH
CH3 CH3

OH
H2SO4/ H2O
Mechanism

+ +
H+
CH3 CH2 CH CH2 CH3 CH2 CH CH3 Not CH3CH2CH2CH2
0 0
2 Carbocation 1 Carbocation
(M ore stable) (Less stable)
+
OH2
+ H2O
CH3 CH2 CH CH3 CH3 CH2 CH CH3
2-Butyl carbocation Oxonium ion
el mojeb y3ni
formal charge no.
H + H
O OH
H2O +
CH3 CH2 CH CH3 CH3 CH2 CH CH3 + H3O
Oxonium ion 2-Butanol

This reaction is acid-catalyzed the acid is not consumed

(C) Addition of Halogens Cl2/CCl4 or Br2/CCl4

Br Br
CCl4/ R.T.
CH3CH CHCH3 + Br2 CH3CH CHCH3

Br
CCl4
+ Br2

Br
(D) Addition of Mercuric acetate (Oxymercuration- Demercuation)
CH3
(1) Hg(OA) 2 / THF/ H 2O
CH3CH2 C CH2 CH3CH2 C OH
(2) NaBH 4
CH3 CH3
2-M ethyl-1-butene 2-Hydroxy-2-methylbutane
(tert-pentanol)

Mechanism OAC OAC

+
Hg Hg
CH3CH2 C CH2 OAC
CH3CH2 C CH2
CH3 Oxymercuration
CH3

H2O

CH2 HgOAC CH2 HgOAC

-HOAC
CH3CH2 C OH CH3CH2 C OH2
+
CH3 CH3
-
OAC
An organomercury intermediate
CH3
NaBH4
Alkene to alcohol ( marko )
CH3CH2 C OH
Demercuration
CH3
(E) Hydroboration of Alkenes (Anti- Markovnikov addition)
alkene to
alkyl alcohol
CH3CH CH2 + H BH2 CH3 CH CH2 BH2
Propene
H
Hydroboration
CH3CH CH2 CH3CH CH2
(CH3CH2CH2)2BH (CH3CH2CH2)3B
Tripropylborane
-
H2O 2/ OH
3 CH3CH2CH2 OH Oxydation
Propyl alcohol
Mechanism

H3C H H3C 
H H3C H

C C C C C C
H H H H
H H H B H H BH2
 Alkylborane
H H H
B The other B-H bonds
Cyclic four-center of alkylborane can undergo
Transition state similar additions;leading finally
H Act as electrophile to a trialkylborane
 CH3 OH
(1) Hg(OAC)2/ THF/ H2O CH3 C CH CH3
(2) NaBH4
CH3

CH3 CH3
(1) (BH3)2/ THF
CH3 C CH CH2 CH3 C CH2 CH2OH
(2) H2O2/ NaOH
CH3 CH3

H2SO4/ H2O
CH3 OH
CH3 C CH CH3
CH3
III- Oxidation of alkenes
(KMnO4) or (OsO4)

 This reaction is Syn-additiom of two hydroxyl groups; the attack

of the 2C atoms of C=C takes place from the same side.

OH OH
Cold
CH3CH CH2 + KMnO4 CH3CH CH2 + MnO2
H2O
Propane 1,2-Propanediol Brown ppt
(Propylene glycol)

OH
Cold
+ KMnO4 + MnO2
H2O

OH
 Mechanism for Syn-addition of alkenes
(Syn Hydroxylation)

C C
O O H2O
C C + MnO 2
Mn O O
- Mn OH OH
O O -
O O
C C
O O
C C H2O
Os C C + Os
O O O O OH OH
Os
O O
 lysis : break

* Ozonolysis of alkenes (Addition of ozone O3)

CH3 H CH3 H
CH3 H
0

C C O3 / - 78 C C C Zn/ H2O / HOAC

C O + O C
CH3 O O H
CH3 H O CH3 H
Ozonide Acetone Formaldehyde

CH3 CH3 CH3

0
1)O3/ - 78 C
C C 2 C O
2)Zn/ H2O/ HOAC
CH3 CH3 CH3

CH3 H CH3 H
0
1)O3 / - 78 C
C C C O + O C
2)Zn/ H2O / HOAC
CH3 CH3 CH3 CH3
Acetone Acetaldehyde
 ALKYNE
(Acetylenes)
M.F. = CnH2n-2
1 2 3 5 7 4 3 2 1 1 2 5
CH3 C C CH2 Cl
3
4 6 4
1-Heptyne 1-Chloro-2-butyne 3-M ethyl-1-pentyne

CH3 CH3
CH3 CH CH2CH2C CH CH3 C CH2 C CH
6 5 4 3 2 1 5 4 3 2 1
CH3
5-M ethyl-1-hexyne 4,4-Dimethyl-1-pentyne

HC CH
Ethyne (acetylene)

Ethynylcyclohexane CH3C CH
( HC C : ethynyl gp) Propyne (methylacetylene)

1 2 3
CH3C CCH3
5 6 7 2-Butyne (dimethylacetylene)
4
1,5-Heptadiyne

* Radicals: Alkynyl
H C C CH3CH2 C C
Ethynyl 1-Butynyl
 PREPARATION OF ALKYNES
1- By the action of ethanolic KOH on ethylene bromide (vicinal dihalide)
The reaction proceeds in two steps.

CH2Br CH2Br + KOH/ Ethanol CH2 CHBr + KBr + H2O

Ethylene bromide
(Vicinal dihalide)

CH2 CHBr + KOH/ Ethanol CH CH + KBr + H2O

Vinyl bromide

2- By the action of KOH/EtOH on ethylidene chloride (Geminal dihalide)

3 KOH
CH2CHCl2 + KOH/ EtOH CH2 CHCl CH CH
Ethylidene chloride
(Geminal dihalide)
3- Using sodamide in liquid ammonia
Br Br MN YOUTUBE
CH CH + 2 NaNH2 CH CH + 2 NaBr + 2 NH3