Lecture9 Alkenes2010
Lecture9 Alkenes2010
CnH2n
• where n is the number of
carbon atoms in the
molecule
Physical Properties
• Physical state -The first lower
member like ethene, propene and
butene are colorless gases.
• Density - lighter than water.
• Solubility - insoluble in water and
soluble in nonpolar organic solvents.
• more reactive than alkanes due to
their double carbon-carbon bond.
• Boiling point -The boiling points
of alkenes gradually increase with
an increase in the molecular
mass.
• The cis isomer ( example cis-2-
butene, b.p.= 3.7°C) is higher in
bpt than its trans isomers
(example, trans-2-butene, b.p.=
1°C)
• Melting point
The melting points of alkenes
increase with an increase in
the molecular mass.
Natural Sources
• Isolated from petroleum.
• Plant material like plant
hormone, like Ethylene – a
natural ripening agent and
Terpenes – found in essential oil.
Some Common Alkene Polymers and their Uses
1. Dehydrohalogenation of Alkyl
halides
2. Dehydration of Alcohol
3. Dehalogenation of Vicinal Halides
4. Reduction of Alkynes
Preparations of alkenes
1. Dehydrohalogenation of alkyl halides
C C + KOH
alcohol
C C + KX + H 2O
Example:
KOH
CH3CH2CH2CH2Cl CH3 CH2 HC CH2
n-butyl chloride 1-butene
- +
KOH is an OH donor use to abstract H
CH3CH2CHClCH 3 KOH
sec - butyl chloride
CH3 HC CHCH3
2 - butene (80%)
+ CH3CH2HC CH2
1 - butene (20%)
Dehydrohalogenation of Alkyl Halides
• Is an Elimination reaction. The term "elimination"
describes the fact that a small molecule is lost
during the process.
Different mechanisms are possible:
– Loss of the LG to form a carbocation, removal of
H+ and formation of C=C bond
– Simultaneous H+ removal, C=C bond formation
and loss of the LG
– Removal of H+ to form a carbanion, loss of the LG
and formation of C=C bond.
2. Dehydration of alcohol
acid
C C C C + H2 O
alkene
H OH
Ease of dehydration of alcohols
3° > 2° > 1°
ex.
H H H H
H2SO 4
H C C H H C C H + H2O
ethylene
H OH
ethyl alcohol
+
acid serves as H donor
H2SO4
CH3CH2CH2CH2OH CH3CH2 HC CH2 CH3 HC CHCH3
H2SO 4
CH3CH2 HC CH3
Al 2O 2 in
CH3 HC CHCH3 + CH3CH2 HC CH2
OH heated tube
C C + Zn C C + ZnX2
X X
dihalides
Example:
Zn
CH3 HC CH CH3 CH3 HC CHCH3 + ZnX2
Br Br
R R
Pd, NiBr
C C syn (cis)
Lindlar
Catalyst H H
R C C R
R H
Na or Li NH3
C C anti (trans)
H R
Reduction of Alkynes
• Reducing Alkynes to form trans or cis
Alkenes.
Using Na/ NH3
Step 1:
Sodium transfer an electron to the alkyne
giving a radical anion.
Step 2: The radical anion removes a proton
from the ammonia in an acid/base
reaction
Step 3:
A second atom of sodium transfers
another electron to the alkyne giving an
anion.
Step 4 :
the anion removes proton from the
ammonia in an acid/base reaction.
Reactions of Alkene
• Halogenation
• Hydration
• Hydrogenation
• Addition of hydrogen Halides
• Addition of sulfuric acid
• Addition of Carbenes
• Addition of Free Radical
• Allylic Hydrogenation • Hydroboration-
• Dimerazation oxidation
• Alkylation • Epoxidation
• Polymerization
• Hydroxylation
• Halohydrins formation
• Ozonolysis
Reactions of Alkenes
Example.
Br2 CCl4
HCH3C CH2 CH3CHBrCH2Br
propene(propylene) 1,2 dibromopropane (propylene bromide)
Halogenations – Addition of
Halogens
• When an alkene is treated at room temperature
with a solution of bromine or chlorine in carbon
tetrachloride or some other inert solvent, the
halogens adds rapidly to the double bond of the
alkene to give the corresponding vicinal dihalide (
two halogens attached adjacent carbons
2. Addition of Hydrogen (catalytic hydrogenation)
Pt, Pd or Ni
C C + H2 C C
H H
Ex.
H2, Ni
HCH3C CH2 CH3CH2CH3
propene(propylene) propane
Hydrogenation of Alkenes
• The relationship between reactants and
products in addition reactions can be
illustrated by the hydrogenation of alkenes
yield alkanes.Hydrogenation is the addition of
H2 to a multiple bond.
3. Addition of hydrogen halides
C C + HX C C HX = HCL, HBr, HI
H X
Ex.
HCH3C CH2 HI
CH3CHICH 3
propene 2 - iodopropane ( isopropyl halides)
Br
H 3C C CH3 Markovnikov addition.
no peroxides
H
2 - bromopropane
HBr
HCH3C CH2 (Isopropyl bromide)
H3C CH CH2
+ HI H3C CHI CH3 actual product
HI
CH2=CHCl CH3CHICl
- - -
vinyl chloride 1 Chloro 1 iodoethane
CH3 CH3
H3CHC=C CH3
+ HI I CCH2CH3
CH3
CH3CH=CHCH3 + HI CH3CHICH2CH3
Addition of hydrogen halides
– In the addition of an acid to the C=C of an
alkene, the hydrogen of the acid attaches
itself to the carbon that already holds the
greater number of hydrogens
– The reactivity of alkene, with halogen
acids is in the order;.
HI > HBr > HCl
4. Addition of sulfuric acid
C C + H2SO 4 C C
H OSO3H
alkyl hydrogen sulfates
Ex.
CH3
63%H2SO 4
H2C CCH3
5. Addition of water. HYDRATION
+
H
C C + HOH C C
H OH
Ex.
OH
+
H2O, H
HCH3C CH2 H3C CHCH3
propene Isopropyl alcohol (2 - propanol)
H3C +
CH3
H2O, H
H3C C CH2 H3C C CH3
Isobutylene CH4
OH
tert - butyl alcohol
Addition of Water - Hydration
– When heated with water in the presence of an
acid catalyst, alkenes yield alcohol ROH.
– The process is called hydration of alkenes because
it involves the addition of water across the double
bond.
– The addition of the HOH across the double
bonded carbon that bears the greater number of
hydrogen atoms and the hydroxyl groups goes to
the other double-bonded carbon
6. Halohydrin formation
C C + X2 + H 2O C C + HX X2 = Cl 2, Br 2
H OH
Ex.
Cl 2, H2O
HCH3C CH2 H3C CH CH2 follow Markovnikov rul
propylene HO Cl
(propene)
propylene chlorohydrin
Sterospecific:
H3C H CH3
C Cl H
Cl2, H 2O
3 - chloro - 2 - butanol
C
H OH
H3C H
cis - 2 - butene CH3
threo (stereospecific)
H CH3 CH3
C H Cl
Cl2, H 2O
C 3 - chloro - 2 - butanol
H3C H OH
H
trans 2 - butene CH3
erythro
7. Dimerization (di = two, mer = part, product contains exactly twice
the # of C & H atom as the original).
CH3 CH3
addition of a hydrogen ion
H 3C C CH2 + H:Br H3C C
+
CH3 + : Br to isobutylene to form
the carbon
H 3C C
+
CH3 + H 3C C CH 2 H3C C CH 2 C
+
CH3 H 3C C CH C CH3
H3C H3C
acid
C C + R H C C
H R
ex.
CH3 CH3
Addition of a hydrogen
ion to form carbocation
H 3C C CH2 + H:B H3C C CH3 + :B
+
CH3 CH3 CH3 CH3 Addition of a
tert-butyl
H3 C C CH2 + H3 C C + H3 C C CH2 C CH3 carbocation to
+ isobutylene
CH3 CH3
Carbocation
abstracts a
CH3 CH3 CH3 CH3 CH3 hydrogen atom with
its pair of electrons
H 3C C CH2 C CH3 + H C CH3 H3 C C CH2 C CH3 + from a molecule of
alkane. This
+ CH3 abstraction of
CH3 CH3 H hydride ion yields
CH3 an alkane of 8
carbons and a new
carbocation to
+C CH3
continue the chain.
CH3
A carbocation may:
oxymercuration demercuration
NaBH4
C C + H2O + Hg(OAc)2 C C C C
mercuric acetate
HO AcOHg HO H
organomercurial cmpd. alcohol
Markovnikov orientation
CH3
CH3
Hg(OAc)2, H2O NaBH4
CH2CH3C CH2 CH2CH3C CH3 Follows Markovnikov
2 - methyl - 1 - butene addition
OH
tert - pentyl alcohol
OH
1 - methylcyclopentene 1 - methylcyclopentanol
CH3 CH3
Hg(OAc)2, H 2O NaBH4
H3C C CH CH2 H3C C HC CH3
CH3 CH3 OH
3, 3 - dymethyl - 1 - butene 3, 3 - dymethyl - 2 - butanol
10. Hydroboration – oxidation
H2O 2
C C + (BH3)2 C C
OH
- C C
Diborane
H B H OH
-
OH
(CH3CH2)3B + 3H2O2 3CH 3CH2OH + B(OH) 3
ethanol boric acid
Mechanism:
C C + H-B C C C C
hydroboration oxidation
B OH
CH3 -
CH3
(BH 3)2 H2O 2, OH
H3C C=CH2 H3C CHCH2OH
Isobutylene Isobutyl alcohol
-
(BH 3)2 H2O 2, OH
CH3CH2CH=CH 2 CH3CH2CH2CH2OH
- -
1 butene n propyl alcohol
11. Addition of free radicals
peroxides
C C + Y Z
or light C C
Y Z
peroxides
RCH CH 2 + CCl 4 RCH CH2 CCl 3
Cl
Mechanism:
peroxides rad.
Cl
Electrophilic addition : Markonikov orientation
H3C
.CH CH2Br
2º free radical
HBr
H3C CH2 CH2Br
Br.
.
HCH 3C CH2
propylene
Polymerization – the joining together of many small molecules to form very large
molecules.
Monomers – the simple compounds form which polymers are made.
Ex.
O 2, heat, pres
nCH2 CH2 H 2C CH2 CH2 CH2 CH2 CH2
or
H2C CH2
polythylene
(plastic material of packaging film)
•5 processes of polymerization
Polyvinyl chloride - use to make phonograph, records, plastic pipes, when plasticized with
high boiling esters – raincoats, shower curtains and coatings for metal and upholstery fabrics.
Peroxide – initiator, required in small amount in polymerization
-Free radical initiator
.
Mechanism:
radCH2 CH
G
.+ H2C CH
G
radCH2 CH
G
CH2 CH
G
. chain propagating step
13. Addition of Carbenes. Cycloaddition
carbenes – derivative of methylene
+ - UV light
H2C N N photolysis CH2 + N2
diazomethans methylene
UV light
H2C C O CH2 CO +
ketene methylene
Methylene exist into 2 different forms
singlet methylene – unshared electrons are paired, less stable
:
& generated first in photolysis : stereospecific addition
CH2 or H
.
:. .. C
..
triplet methylene – unshared electrons are not paired,
free radical (diradical) : nonstereospecific addition
H :.. C H
Cycloaddition: addition of the carbon – carbon double bond
light
HCH3C CHCH3 +
CH2N2 HCH3C CHCH3 + N2
2 - butene diazomethane
CH2
1, 2 - dimethycyclopropane
And in liquid
CH2 CH2
Singlet methylene
Stereospecific
Electrophilic addition
Electron deficient and
can find electrons at
. .+
CH2 C C C
.
C
the C-C double bondingle
C C
CH2 . CH2
Non – stereospecific: cis/trans2 – butene + CH2N2 both cis and trans 1,2 -
dimethylcyclopropane
Triplet methylene
Non - Stereospecific
Free radical addition
ff. by addition
Methylene undergoes intersection
C H + CH2 C CH2 H
Cl Cl
3, 3 - dichloro - 1, 2 - dimethylcyclopropane
Mechanism:
..-+ .. .. -
+ .. Reaction involves
a divalent carbon
..
t - BuO H CCl3 CCl3 t - BuO H
CCl3
- ..CCl2 + Cl -
compound, a
derivative of
methylene:
dichlorocarbene dichlorocarbene:
CU2.
HCH3C CH3CH .
+. CCl 2 HCH3C
Generated in 2
CHCH3 steps, initiated by
attack on
chloroform by the
C strong base tert-
butoxide ion and
Cl Cl then adds to the
alkene.
Because of the presence of halogen atom, the singlet form is the more
stable form of dichlorocarbene and is the one adding to the double bond.
Addition of Carbenes
• Carbenes are intermediates of the general
formula CH2:. The derivatives of methylene
(CH2) are the carbenes.
• Methylene is formed by the photolysis of
either diazomethane, CH2N2 or ketene,
CH2=C=O.
14. Hydroxylation. Glycol formation
OH OH
Example.
cold, dil. KMnO4 or HCO2OH
HCH 3C CH2 H 3C CH CH2 + 2MnO2
propylene OH OH
1,2 - propanediol (propylene glycol)
HO OH
- -
cis 1,2 cyclopentanediol
HCO2OH -
OH + HO anti hydroxylation
OH HO
- -
trans 1,2 cyclopentanediol
15. Halogenation. Allylic substitution ( same mechanism with substitution in alkene
heat
H C C C + X2 X C C C X2 = Cl 2, Br 2
low conc.
Ex.
HCH3C CH2 Cl 2, 600º
Cl - CH 2CH CH2
propylene allyl chloride
Br
+ NBS
N - bromosuccinimide
cychlohexene 3 - bromocyclohexene
-
CH2=CH CH3
- -
alkene like site of addition alkane like site of substitution
-
CH2=CH CH3
-
heterolytic attack, addition Free radical attack, substitution
Can we direct the attack to just one of these sites? Yes, by our choice of
rxn. Conditions.
Conditions:
1.alkenes undergo substitution by halogen at high temp. or under the influence of
UV light, generally in gas phase.
2.it can also undergo addition of halogen at low temp. in the absence of light and
generally in liquid state(phase).
low T
H3C CH CH2
CCl4 soln
heterolytic add'n
Cl Cl
Cl2 1,2 - dichloropropane
H3C CH CH2
propylene
O
O
C
C CH2 N H
HBr +
CH2 N Br Br 2 + CH2 C
CH2 C
O
O
NBS succinimide
C H
vinylic hydrogen: hard to abstract
C H
Ease of abstraction of hydrogen atoms: Allylic >3º > 2º > 1º > CH4 > Vinylic
Ease of formation of free radicals: allyl > 3º > 2º > 1º > CH3. > vinyl
Example:
NBS
CH3(CH2)3CH2CH2CH=CH2
16. Ozonolysis (Cleavege rxn)
O H2O, Zn
C C + O3 O O C O + O C
ozone aldehyde ketone
O O
ozonide
Cleavage – a rxn in which the double bond is completely broken and the alkene
molecules converted into 2 smaller molecule.
Reducing agent (Zn) – prevent formation of hydrogen peroxide
will not react with aldehyde and ketone (aldehyde are often
converted to acid, RCOOH for ease of isolation.)
O3 H2O, Zn
CH3CH2CH=CH2 CH3CH2CHO + CH2=O
CH3 H3C H
H3C C=CH2
O3 H2O, Zn
H3C C=O + O CH
H2O, Zn O3
CH3CH2CH2CH=CHCH3
CH3CH2CH2CHO + CH3CHO
H H H H
H2O / Zn O3
CH 2CH 3C O + O C CH 2CH3 CH2CH3C C CH2CH3
aldehydes 3 - hexene
H CH3 H CH3
H2O / Zn O3
CH2CH3C O + O C CH3 CH2CH3C C CH3
aldehydes ketone 2 - methyl - 2 - pentene
KMnO4 NaIO4
C C C C acids, ketones. CO2
cold, dil.
OH OH
CH3 CH3
KMnO 4
CH3COOH + O C CH3
NaIO 4
H3C CH C CH3
carboxylic acid ketone 2 - methyl - 2 - butene
KMnO4
CH3CH2CH2COOH + CO2
NaIO4
HCH 2CH2CH3C CH2
carboxylic acid carbon dioxide
Cleavage of cycloalkenes
CH 2
O3 H2O, Zn H 2C CHO
di - aldehyde
H 2C CHO
CH2
CH 2
H 2C CH
H 2C CH
CH2 CH2
KMnO 4 H2C COOH
di - acid
NaIO 4 H2C COOH
CH2
18. Epoxidation of Alkenes
O O