Chapter 3
Alkenes and Alkynes
Teaching Objectives and Requirements
Understand: Unsaturated Hydrocarbons,
Hydrogenation. Grasp: Geometric Isomer
s, E,Z Designation, Nomenclature, Oxidati
on, Electrophilic Addition of Hydrogen Hali
des, Sulfuric Acid, Halogens, Markovniko
v’s Rule. Moderately grasp: Mechanism of
Addition to Alkenes.
Key points and Areas of Difficulty
Electrophilic Addition, Markovnikov’s Rule
, Oxidation.
3.1 Unsaturated hydrocarbons
Carbon-carbon multiple bonds
Fewer hydrogen atoms than alkane or c
ycloalkane—unsaturated
CH3 CH3 CH2 CH2 CH CH
Alkenes—a carbon-carbon double bond
Alkynes—a carbon-carbon triple bond
Alkadienes—conjugated dienes
3.1 Unsaturated hydrocarbons
Two double bond units are joined by one s
ingle bond
CH3 Cl
CH2 C CH CH2 CH2 C CH CH2
isoprene chloroprene
Alkenes
Simplest alkene, C2H4,commonly called et
hylene,IUPAC name ethene
Suffix –ene
3.1 Unsaturated hydrocarbons
Six atoms of ethene are located in the same plane
H H H H
C C C C
H H H H
representation in representation perpendicular
the plane formula
General of the page
CnH2n to the plane of the page
Alkynes
Simplest alkyne, C2H2,commonly called acetylene,I
UPAC name ethyne
3.1 Unsaturated hydrocarbons
Suffix –yne
Four atoms of acetylene are located in a s
traight line
General formula CnH2n-2
terminal alkyne internal alkyne
R C C H R C C R
monosubstituted alkyne disubstituted alkyne
3.2 Geometric Isomerism
No free rotation of double bond
Different groups bond to the double bond ca
rbon
Different spatial or geometric arrangements
Y Y Y X
C C and C C
Geometric
X isomers
X X or cis-trans
Y
isomers
Two different groups for each double-bonde
d carbon atom
3.2 Geometrism Isomerism
Two same groups bond to two carbons of d
ouble bond
same groups on 2 carbons
H H
different different
C C groups on 1 carbon
groups
Cl Cl
1,2-dichloroethene
These two same groups on the same side
—cis,on the two side—trans
H Cl H H
C C C C
Cl
Cl H Cl
trans-1,2-dichloroethene cis-1,2-dichloroethene
3.2 Geometrism Isomerism
One of the unsaturated carbon atoms is at
tached to two identical groups—no cis-tra
ns isomerism
H H Cl H
identical idential identical
different C C groups
C C groups groups
groups Cl
Cl H H
chloroethene 1,1-dichloroethene
Geometrism isomers,different physical pro
perties
3.3 The E,Z Designation of
Geometric Isomers
Tri- and tetrasubstituted alkenes-E,Z syst
em of nomenclature
Sequence rules to assign priorities to the
groups,low or high
Higher priority groups—same side:Z isom
er
high high high low
C C C C
low low low high
Z isomer E isomer
3.3 The E,Z Designation of
Geometric Isomers
Higher priority groups—oppsite side:
E isomer
The same for lower groups
Sequence rules
High atomic-number atom—high priority
Br>Cl>F>O>N>C>H
low priority
high priority Br CH2CH2Br
C C
low priority Cl F high priority
3.3 The E,Z Designation of
Geometric Isomers
Compare from first atom bonded directly t
o carbons of double bond,then second,…
tert-butyl>isopropyl>ethyl>methyl
CH3 H
CH3 C CH3 CH2 CH2 C
H H
isopropyl butyl
Double bond=two single bond,so for triple
bond
C O is treated as C O
O C
replicated atoms
3.4 Nomenclature of Alkenes and
Alkynes
Substituents common names
CH2 CH CH2 CH CH2 CH C CH2
vinyl allyl propargyl
IUPAC names of alkenes
Parent:longest continuous chain,contain doubl
e bond
7 8
CH2 CH3
5 6
CH3 CH2 CH CH3
3 4
C C
1 2
CH3 CH2 CH3
Stem name similar to alkane,ene replace ane
3.4 Nomenclature of Alkenes and
Alkynes
Smallest number for carbon of double bond
5 6 7 1
CH3 CH2 CH2 CH3 CH3 CH3
3 4 3 2
C C C C
1 2 5 4
CH3 CH2 CH3 CH3 CH2 CH3
3-heptene not 4-heptene 2,3-dimethyl-2-pentene not
3,4-dimethyl-2-pentene
E or Z in parentheses,in front of the name Positi
on number,name of substituents
5 6
CH3 CH2 CH3
3 4
C C
1 2
CH3 CH2 CH3
(E)-3,4-dimethyl-3-hexene
3.4 Nomenclature of Alkenes and
Alkynes
Position number of double bond,then pare
nt name
Di,tri in front of –ene,show more than one
double bond
1 2 3 4 5 6 7
CH2 CH CH CH CH CH CH3
1,3,5-heptatriene
Cycloalkene,double-bonded carbon atoms
(1 or 2),smallest number of substituent
3.4 Nomenclature of Alkenes and
Alkynes
2 3 2
1
3 CH 1
3 4 CH3
5
4 5 6
3-methylcyclopentene 1-methylcyclohexene
IUPAC names of alkynes
yne replace ene,similar to alkenes
6 5 4 3 2 1 6 5 4 3 2 1
CH3 CH2 CH2 C C CH3 CH3 CH2 C C CH CH3
CH3
2-hexyne 2-methyl-3-hexyne
3.4 Nomenclature of Alkenes and
Alkynes
Multiple triple bonds:diyne,triyne and so on
Compounds with both double and triple bonds a
re enynes,not ynenes
Start numbering from the end nearest the first m
ultiple bond
Double bonds are assigned lower numbers
6 5 4 3 2 1 1 2 3 4 5
CH3 C C CH2 C C H CH2 CH CH2 C C H
1,4-hexadiyne 1-penten-4-yne
3.5 Hygenation of Alkenes and Al
kynes
Reduction of alkenes
React with hydrogen gas
Double bond changes to single bond
Catalyst:nickel or platinum
This double bond is changed into a single bond.
Pt/C
CH3(CH2)5CH CH2 + H2 CH3(CH2)5CH2 CH3
1-octene octane
C-O double bond won’t be reduced
3.5 Hygenation of Alkenes and Al
kynes
O O
Pt/C
CH3 C CH2 CH2 CH CH2 + H2 CH3 C CH2 CH2 CH2 CH3
Same face addition of two hydrogen atoms
Pd/C
+ H2 H H
CH3 CH3 CH3 CH3
1,2-dimethylcyclopentene cis-1,2-dimethylcyclopentane
Reduction of alkynes
Similar to alkenes
3.5 Hygenation of Alkenes and Al
kynes
Two molar equivalents of hydrogen gas—s
aturated compounds
This triple bond is changed into a single bond.
Pt/C
CH3(CH2)6C CH + 2 H2 CH3(CH2)6CH2 CH3
1-nonyne nonane
Alkene product by Lindlar catalyst—cis ad
dition
H2 CH3(CH2)3 (CH2)3CH3
CH3(CH2)3C C(CH2)3CH3 C C
Lindlar
catalyst H H
5-decyne cis-5-decene
3.5 Hygenation of Alkenes and Al
kynes
Reduction with lithium metal in liquid
ammonia—trans addition
H
[Link]/NH3 CH3(CH2)3
CH3(CH2)3C C(CH2)3CH3 C C
2. H2O
H (CH2)3CH3
5-decyne trans-5-decene
3.6 Oxidation of Alkenes and
Alkynes
Hydroxylation of alkenes
Potassium permanganate(KMnO4)
Mild condition:basic, low temperature
Product of two neighbor hydroxyl groups
On carbons of the original double-bond unit
KMnO4
CH3(CH2)5CH CH2 CH3(CH2)5CH CH2 + MnO2
NaOH/H2O
OH OH
1-octene 1,2-octanediol
3.6 Oxidation of Alkenes and
Alkynes
Potassium permanganate:purple solution
Manganese dioxide:a brown solid
Phenomenon:purple change to brown
Test the presence of double bond by color
Ozonolysis of alkenes and alkynes
Ozone,O3,react in two steps
1. O3
C C + C O + O C
2. Zn/H3O
carbonyl compounds
3.6 Oxidation of Alkenes and
Alkynes
Product for alkenes:carbonyl compounds
Without concern the structure,just keep it
Change the one C of carbon-carbon
double bond with O
Product for alkynes:carboxylic acids
Similar to alkenes:two O replace one C
1. O3
R C C R' +
R CO2H + R' CO2H
2. Zn/H 3O
1. O3
R C C H +
R CO2H + CO2
2. Zn/H3O
3.7 Addition Reactions of
Alkenes and Alkynes
Symmetrical reagents consist of two identica
l groups,Br2
Unsymmetrical reagents consist of two differ
ent groups,HCl and H2O
CH2 CH2 + Br Br Br CH2 CH2 Br
CH2 CH2 + H Cl H CH2 CH2 Cl
CH2 CH2 + H OH H CH2 CH2 OH
Addition of halogens
Reddish bromine give colorless product
Determine the unsaturated compounds
3.7 Addition Reactions of
Alkenes and Alkynes
CCl4
CH3(CH2)5CH CH2 + Br2 CH3(CH2)5CH CH2
Br Br
colorless red colorless
Chlorine also adds to double bonds
Cl Cl
CCl4
CH3(CH2)3 C C H + Cl2 CH3(CH2)3 C C H
Cl Cl
1-hexyne 1,1,2,2-tetrachlorohexane
Cl
CCl4
CH3(CH2)3 C C H + Cl2 CH3(CH2)3 C C H
Cl
Iodine:bad yield
1-hexyne (E)-1,2-dichlirohexane
3.7 Addition Reactions of
Alkenes and Alkynes
Fluorine:too reactive to control
Addition of hydrogen halides
HX is unsymmetric reagent
For symmetric alkenes
H and X add to any carbon of double bond
CH2 CH2 + H Br H CH2 CH2 Br + Br CH2 CH2 H
equivalent identical structures
atoms
3.7 Addition Reactions of
Alkenes and Alkynes
For unsymmetric alkenes, two choices
Br
CH3 CH CH2 + H Br CH3 CH CH2 H
propene 2-bromopropene
H
CH3 CH CH2 + H Br X CH3 CH CH2 Br
propene 1-bromopropene
Markovnikov’s Rule
H adds to carbon with more H atoms
No hydrogen atoms Two hydrogen atoms
on this carbon atom on this carbon atom
CH3 H Cl
C C + H Cl CH3 C CH2 H
CH3 H CH3
2-methyl-1-propene 2-chloro-2-methylpropane
3.8 Mechanism of Addition
Reactions
π electrons-a nucleophile (nucleus lover)
Accept an electrophile (electron-loving species)
HBr may be considered as H+ and Br–
H+ ,an electrophile,reacts first with π bond
A positively charged species-carbocation
H H
H H
C C +
+ H C C
CH3 H
H CH3 H
nucleophile electrophile isopropyl carbocation
3.8 Mechanism of Addition
Reactions
Positively charged C+ attaches to negative
ly charged Br–
H H Br
Br- + C C CH3 CH CH2 H
H
CH3 H
nucleophile electrophile 2-bromopropane
For propene,H+ has two possible attachm
ent to carbon atoms
H H H H
H+ + C C C C
H
CH3 H H CH3
electrophile nucleophile propyl carbocation
3.8 Mechanism of Addition
Reactions
3.8 Mechanism of Addition
Reactions
3.8 Mechanism of Addition
Reactions
Form propyl or isopropyl carbocations
More stable: isopropyl carbocation
More stable carbocation forms product
So 2-bromopropane not 1-bromopropane
Alkyl can give electrons to positive charge
More substituted carbocation more stable
H H H R
H C+ < R C+ < R C+ < R C +
H H R R
methyl primary secondary tertiary
increasing stability
3.9 Hydration of Alkenes and
Alkynes
H2O fits the general class of HX (H—OH)
In accordance with Markonikov’s rule
OH
CH3 CH CH2 + H OH CH3 CH CH2 H
propene 2-propanol
H
CH3 CH CH2 + H OH X CH3 CH CH2 OH
propene 1-propanol
Hydration of alkynes produces carbonyl comp
ounds
In the presence of mercuric sulfate catalyst
Enol=en+ol,alkene+alcohol
3.9 Hydration of Alkenes and
Alkynes
Enol convert to more stable carbonyl
H2SO4 OH
R C C H + H OH
HgSO4 R C CH2
an enol
O
OH
R C CH3
R C CH2
an enol a ketone
more substituted less substituted
carbon atom carbon atom
O
H2SO4
C C H + H OH C CH3
HgSO4
3.10 Preparation of Alkenes and
Alkynes
Dehydration of alcohols
Requires strong concentrated acids sulfuric acid, H2SO4,
or phosphoric acid, H3PO4
Elimiantion reaction
These atoms are
eliminated
H OH H H
H2SO4
H C C C H H C C C H
H H H H H H
A single bond is converted
Breaking theinto
carbon-oxygen
a double bond. bond
3.10 Preparation of Alkenes and
Alkynes
Breaking carbon-hydrogen bond on an
adjacent carbon atom
For 2-butanol,two different carbon atoms are
adjacent to the OH-bearing carbon atom
Elimination of water can
occur in two possible ways
H OH H H H OH H H
H C C C C H H C C C C H
Each Hcould release aH hydrogen
H H H H H H
atom
3.10 Preparation of Alkenes and
Alkynes
Produce a mixture of products
The greater number of alkyl groups attach
ed to the double bond predominates
Main product:the more substituted alkene
Zaitsev’s rule:give the more substituted do
uble bond
OH
H2SO4
CH3CHCH2CH3 CH2 C CH2CH3 + CH3 C C CH3
H H H
3.10 Preparation of Alkenes and
Alkynes
3-pentanol,yield cis- and trans-2-pentene
The trans isomer is the major product,also
the more stable isomer
In the trans isomer the alkyl groups are w
ell separated
In the cis isomer the alkyl groups are near
OH CH3CH2 CH3 CH3CH2 H
H2SO4
CH3CH2CHCH2CH3 C C + C C
H H H CH3
cis-2-pentene trans-2-pentene
(25%) (75%)
3.10 Preparation of Alkenes and
Alkynes
The proximity of the alkyl groups cause steri
c hindrance
The groups repel each other
Trans isomer is more stable, predominates
Dehydrohalogenation
Elimination of the elements H and X as in H
Cl or HBr from adjacent carbon atoms
B- + H C C X C C + HB + X
-
3.10 Preparation of Alkenes and
Alkynes
Product is alkene
Require a base,represented by B-
Usuaslly alkoxide ion such as C2H5O-
CH2Cl CH2
CH3CH2O-Na+
H CH CH OH
3 2
More highly substituted alkene predominate
Trans isomers are favored over cis isomers
3.10 Preparation of Alkenes and
Alkynes
Br CH3 H CH2CH3
CH3CH2O-Na+ CH3
CH3CCH2CH3 C C + C C
CH3CH2OH CH3
CH3 H H CH3
2-methyl-2-butene 2-methyl-1-butene
(70%) (30%)
Elimination reactions of dihalides
The reactant is a vicinal dihalide
Two molar equivalents of HX must be elim
inated
3.10 Preparation of Alkenes and
Alkynes
Produce alkynes (contain two π bonds)
Stronger base than alkoxide ion is require
d
Cl H
NH2-
CH3(CH2)3 C C H CH3(CH2)3 C C H
NH3
H Cl
1,2-dichlorohexane hexyne
3.11 Alkadienes
Conjugated alkadienes
Chemically different from simple alkenes
Two double-bonded units
Separated by only one single bond
Isolated or nonconjugated alkadienes
Separated by more than one single bonds
CH3 CH CH CH CH2 CH2 CH CH2 CH CH2
1,3-pentadiene 1,4-pentadiene
(a conjugated diene) (a nonconjugated diene)
3.11 Alkadienes
Electrophilic conjugate addition
Nonconjugated alkadienes similar to alkene
Br
HBr
CH2 CH CH2 CH CH2 CH3 CH CH2 CH CH2
1,4-pentadiene 4-bromo-1-pentene
Br Br Br
HBr
CH3 CH CH2 CH CH2 CH3 CH CH2 CH CH3
Conjugated alkadienes:two products (HBr)
2,4-dibromopentane
1,2-addition product
Double bond between C-1 and C-2 atoms
1,4-addition product
3.11 Alkadienes
Double bond between C-2 and C-3 atoms
H Br H Br
HBr
CH2 CH CH CH2 CH2 CH CH CH2 + CH2 CH CH CH2
3-bromo-1-butene 1-bromo-2-butene
(1,2-addition,70%) 1,4-addition,30%)
Allylic carbocation—2 resonance structure
s
Structures change each other
Either terminal carbon atom could react wit
h a nucleophile
CH2 CH CH2 CH2 CH CH2
3.11 Alkadienes
Two products are identical
Conjugated diene:two resonance structure
of allylic-type ion
Nucleophile can react to two resonance st
ructures
Two products produce
H H
H+ + CH2 CH CH CH2 CH2 CH CH CH2 CH2 CH CH CH2